Sample records for rutile a-tio2 experimental

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO2 and ZrO2; Al/(Na + K) molar 1.2] at a pressure of 10 kbar and temperatures of 1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO2 contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4-7.0 wt%. TiO2 contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO2 concentrations (0.2-1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO2 in rutile ( {Xnolimits_{{{{ZrO}}_{ 2} }}^{{rt}} } ) in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of 1,400 to 675 °C) yields the following temperature-dependent expression: {{ln}}( {mathop X{{{{ZrO}}_{ 2} }}^{{rt}} } ) + {{ln}}( {a_{{{{SiO}}2 }} } ) = 2.638(149) - 9969(190)/T({{K}}) , where silica activity a_{{{{SiO}}2 }} in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and Xnolimits_{{{{ZrO}}2 }}^{{rt}} . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of 100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for a_{{{{SiO}}2 }} and a_{{{{TiO}}2 }} for each experiment, zircon Ti concentrations (ppm) can be related to

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: {Mathematical expression} have been calibrated in the range 800-1100?? C and 12-26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs40-70, using Ag80Pd20 capsules with {Mathematical expression} buffered at or near iron-wu??stite. Ilmenite compositions coexisting with orthopyroxene are {Mathematical expression} of 0.06 to 0.15 and {Mathematical expression} of 0.00 to 0.01, corresponding to KD values of 13.3, 10.2, 9.0 and 8.0 (??0.5) at 800, 900, 1000 and 1100?? C, respectively, where KD=(XMg/XFe)Opx/(XMg/XFe)Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models

Most coarse detrital rutile is derived from high-grade metamorphic rocks. Contrary to a conventional assumption, independent rutile grains are particularly rare in igneous rocks except alkalic rocks. The use of rutile in the zircon-tourmaline-rutile index of mineralogic maturity is only partially valid, owing to its restricted provenance. -Author

The adsorption and reaction of formaldehyde (CH2O) on the oxidized rutile TiO2(110) surface were studied by temperature programmed desorption (TPD), scanning tunneling microscopy (STM), infrared reflection-absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. The experimental and theoretical data reveal the presence of various species depending on the temperature and coverage. After formaldehyde adsorption on TiO2(110) at 65 K, the multilayer CH2O was detected, which desorbs completely upon heating to 120 K. The isolated CH2O monomer was identified after submonolayer adsorption at low temperatures (45-65 K), in which CH2O is bound to the surface Ti5c sites via σ-donation and adopts a tilted geometry. With heating to higher temperatures the CH2O monomers remain stable up to 70 K and then undergo coupling reactions to form paraformaldehyde (polyoxymethylene, POM) at the Ti5c rows. The POM chain is oriented primarily along the [001] direction in a slightly disordered configuration. POM becomes the predominant species at 120 K and is decomposed releasing CH2O at about 250 K. In addition, dioxymethylene (DOM) was detected as minority species formed via reaction of Ti5c-bound CH2O with both neighboring O2c along the [1-10] direction and oxygen adatoms (Oad) at Ti5c sites along [001] on the oxidized TiO2(110) surface.

Multiphoton effects are investigated in crystalline rutile TiO(,2) using Nd:YAG laser photons. The 1.06 micron laser is operated in Q-switched mode with intensities up to 1.4 x 10('6) watts/cm('2) on the rutile crystal. Photoconductivity measurements provide data indicating a mixture of modes for electrons to be photoionized. Assuming aluminum impurity as the contributing sites, the first order photionization cross section is found to be 1.5 x 10('-26) cm('2) and second order cross section is found to be 7.7 x 10('-51) cm('4)-s. No appreciable change in cross section is observed for circular versus linear polarization of the laser. Observations of the photo-emission of the laser illuminated crystal provide radiative relaxation times on the order of 100 nanoseconds with emission peaks at 4500 and 5000 angstroms plus a near infrared continuum out to 1 micron. The thermoluminescence of rutile shows a number of trapping levels between 0.4 and 0.8 eV below the conduction band. These are attributed to an aluminum impurity.

The aim of the present work is to elucidate crystallization and growing process of rutile crystals in Ti-bearing blast furnace slag. The samples were taken from the liquid slag and quenched at once at elevated temperatures in order to analyze phase transaction of titanium and grain size of rutile crystals. Crystallization and growing kinetics of rutile crystals under elevated temperature conditions were calculated, and the crystallization process of rutile crystals under isothermal conditions was expressed by Avrami equation. The effects of experimental parameters, such as experimental temperatures, SiO2 addition, cooling rate, crystal seed addition and oxygen flow, were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), the optimal conditions for rutile crystals to grow up were obtained. Distribution and movement state of rutile crystals in the slag were analyzed.

A light scattering particle size test which can be used with materials having a broad particle size distribution is described. This test is useful for pigments. The relation between the particle size distribution of a rutile pigment and its optical performance in a gray tint test at low pigment concentration is calculated and compared with experimental data.

Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions.

The Roseland Anorthosite, located in Nelson and Amherst Counties, VA, was emplaced immediately prior to or during the Grenville orogeny (1045±44 Ma). The anorthosite contains large (>0.5 mm) magmatic rutile crystals within a contaminated zone <100 meters wide along a contact with older granulite-facies gneisses. An OH-in-rutile oxybarometer (Colasanti 2007 GCA 71(15s) A181) was applied to rutile crystals from Roseland in order to evaluate the use of this experimentally-calibrated technique for natural samples. Doubly-polished sections of single rutile crystals were analyzed for hydroxyl (OH) concentrations using polarized FTIR spectroscopy. The average OH concentration is 53±36 ppm H2O by wt. in rutile from the Roseland Quarry near the Tye River and 138±57 ppm for rutile from a roadcut near the Piney River. OH concentrations vary by up to 15 ppm from core to rim within a single crystal, with some crystals showing higher OH concentrations in the rim and others containing higher concentrations within the core. No zoning of trace chemical components is observed within single rutile grains, and the composition of the rutile from both locations is nearly uniform (0.23-0.33 wt% FeO; 0.10-0.13 wt% Nb2O5; 0.14-0.17 wt% ZrO2; 0.02-0.09 wt% Al2O3; 0.03-0.05 wt% Cr2O3). Rutile OH concentration is not correlated to the concentration of Fe, Al, Cr, or charge deficiency (total trivalent cations). Assuming magmatic temperatures of ~850-950°C (Herz 1987 USGS Prof. Paper 1371), the OH-in-rutile oxybarometer predicts that the Roseland Anorthosite magma had an fO2 close to the MH buffer (5-6 log units above FMQ). An alternative explanation is that, regardless of the initial fO2 of the magma, slow cooling after peak Grenville metamorphism resulted in the low OH concentrations preserved in the rutile, since equilibrium OH concentration decreases exponentially with decreasing temperature. Although the OH- in-rutile oxybarometer is not strongly dependent upon water activity, low

Biological studies of two titanium dioxide polymorphs, rutile and anatase, have produced conflicting results. Generally, the in vivo and in vitro methods used to evaluate pneumoconiotic dusts have shown the polymorphs to be inert, but occasionally both minerals have been reported to produce effects consistent with biologically active minerals. Many of these reports failed to specify which polymorph was used experimentally. While this limited the value of the data, the problem was further compounded by the variation in the surface properties of each polymorph depending on whether the specimen was a naturally occurring mineral or was made synthetically. Five naturally occurring and 11 synthetically produced titanium dioxide specimens were studied. The physical characterisation of each specimen entailed the determination of the polymorph type(s) by continuous scan x ray diffraction and the size distribution by transmission electron microscopy. The ability of each specimen to lyse erythrocytes was determined and compared with quartz. Only two, both synthetic rutiles, were found to be active. The hydrogen bonding ability of the surfaces of these rutiles were compared with inert rutile and quartz. The binding properties of the active rutile have been found to be consistent with those properties associated with biologically active quartz. The surface properties of rutile are the determinants of its activity. Because natural and synthetic rutiles possess different surface properties, they display different activities. Images PMID:3676122

This report documents work conducted in FY13 on electrical discharge experiments performed to develop predictive computational models of the fundamental processes of surface breakdown in the vicinity of high-permittivity material interfaces. Further, experiments were conducted to determine if free carrier electrons could be excited into the conduction band thus lowering the effective breakdown voltage when UV photons (4.66 eV) from a high energy pulsed laser were incident on the rutile sample. This report documents the numerical approach, the experimental setup, and summarizes the data and simulations. Lastly, it describes the path forward and challenges that must be overcome in order to improve future experiments for characterizing the breakdown behavior for rutile.

The incorporation of zirconium into the mineral rutile (TiO2) has been both empirically and experimentally calibrated as a measure of rutile crystallization temperatures (Watson et al., 2006). This temperature sensitive system has been employed as a geothermometer with applications to a number of different geologic settings and rock types. Experimentally measured kinetics for Zr diffusion in rutile (Cherniak et al., 2007) indicate that Zr can be lost to temperature dependent diffusion, warranting further investigation of the geologic significance of calculated temperatures. Coupling diffusion kinetics with numerical solutions to the diffusion equation provides a means to forward model the time and temperature dependency of the system. Modeled results indicate a strong dependency of Zr concentration in rutile on both: 1) initial cooling rate following high-temperature metamorphism/crystallization and 2) temperature and duration of long-term geologic residence. Zr concentrations measured in rutile from lower crustal xenoliths that resided at 25-45 km depths for 2000 My, reveal Zr concentrations in the approximate grain center that are consistent with temperatures measured by independent thermometers. Forward models for Zr diffusion show that preserving a Zr record of these initial temperatures in the center of a rutile crystal with a 50 μm radius requires rapid cooling (> 300 °C/Ma) from magmatic/metamorphic temperatures followed by a long-term residence (2000 My) at temperatures < 550 °C. This provides a new way to determine cooling rates between 900 and 500 °C and for constraining the temperature of the deep crust. Modeled temperature-time paths using combined rutile Zr and U-Pb geochronological data permit evaluation/refinement of published diffusion kinetics. Properly quantified, this system can be utilized as a high temperature geo-speedometer: a powerful tool for evaluating heat transfer rates at these very high and often unconstrained temperatures.

The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

Titanium dioxide (TiO(2)) rutile nanoparticles were synthesized at temperatures below 100 °C using a gel-sol process that provides control of the final particles' characteristics, such as the nanoparticle size, morphology, crystal structure and crystallinity. The synthesized rutile nanoparticles were analyzed using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the gel-sol process allows control over the final nanoparticle characteristics with the proper choice of reaction parameters. The most profound influence on the nanoparticles' properties is achieved by the type and concentration of the acid used in the reaction mixture. The gel-sol synthesis resulted in anisotropic rutile nanoparticles that are 60-160 nm long, depending on the reaction parameters, and have an aspect ratio of about 5. A reaction mechanism is presented, explaining the influence of various reaction parameters on the characteristics of the TiO(2) nanoparticles.

This patent describes a method for separating a mixture of minerals comprising at least zircon, ilmenite and rutile. It comprises adding an acid solution to the mixture to acidify to a pH of between about 2.0 and 6.0; adding starch to the mixture to depress the ilmenite and the rutile; adding a source of fluoride ions to the mixture to provide a negative surface charge on the zircon surface to activate the zircon; adding an amine cationic collector to the mixture to float the activated zircon; subjecting the mixture containing the added acid solution, the fluoride ions, the starch and the cationic collector, to froth flotation; and withdrawing a float product comprising the zircon and a sink product comprising the ilmenite and rutile.

Mineralogical studies and U-Pb dating have been carried out on rutile included in peridotitic and eclogitic garnets from the Internatsionalnaya pipe, Mirny field, Siberian craton. We also describe a unique peridotitic paragenesis (rutile + forsterite + enstatite + Cr-diopside + Cr-pyrope) preserved in diamond from the Mir pipe, Mirny field. Compositions of rutile from the heavy mineral concentrates of the Internatsionalnaya pipe and rutile inclusions in crustal almandine-rich garnets from the Mayskaya pipe (Nakyn field), as well as from a range of different lithologies, are presented for comparison. Rutile from cratonic mantle peridotites shows characteristic enrichment in Cr, in contrast to lower-Cr rutile from crustal rocks and off-craton mantle. Rutile with Cr2O3 > 1.7 wt% is commonly derived from cratonic mantle, while rutiles with lower Cr2O3 may be both of cratonic and off-cratonic origin. New analytical developments and availability of standards have made rutile accessible to in situ U-Pb dating by laser ablation ICP-MS. A U-Pb age of 369 ± 10 Ma for 9 rutile grains in 6 garnets from the Internatsionalnaya pipe is consistent with the accepted eruption age of the pipe (360 Ma). The equilibrium temperatures of pyropes with rutile inclusions calculated using Ni-in-Gar thermometer range between 725 and 1030 °C, corresponding to a depth range of ca 100-165 km. At the time of entrainment in the kimberlite, garnets with Cr-rich rutile inclusions resided at temperatures well above the closure temperature for Pb in rutile, and thus U-Pb ages on mantle-derived rutile most likely record the emplacement age of the kimberlites. The synthesis of distinctive rutile compositions and U-Pb dating opens new perspectives for using rutile in diamond exploration in cratonic areas.

Recent breakthrough of novel hierarchic materials, orchestrated through oriented attachment of crystal subunits, opened questions on what is the mechanism of their self-assembly. Using rutile-type TiO2, synthesized by hydrothermal reaction of Ti(IV)-butoxide in highly acidic aqueous medium, we uncovered the key processes controlling this nonclassical crystallization process. Formation of complex branched mesocrystals of rutile is accomplished by oriented assembly of precipitated fibers along the two low-energy planes, i.e. {110} and {101}, resulting in lateral attachment and twinning. Phase analysis of amorphous material enclosed in pockets between imperfectly assembled rutile fibers clearly shows harmonic ordering resembling that of the adjacent rutile structure. To our understanding this may be the first experimental evidence indicating the presence of electromagnetic force-fields that convey critical structural information through which oriented attachment of nanocrystals is made possible. PMID:27063110

The surface structures of rutile TiO2(114) have been studied using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Depending on the sample preparation, the surface exhibits many complicated local nanostructures, e.g., dot-like, missing row, row-like (1 × 3), and twin dotted (2 × 2) structures. After several cycles of sputtering and high-temperature annealing, all samples exhibit triangular pyramidal structure. Microfaceted structural models, which are composed of combinations of {111} and (001) microfacets, can explain all experimental results as well as the structural variety. The calculated STM images are in good agreement with the experimental results. The decreasing density of dangling bonds, the increasing coordination number, and the evolution of non-polar structures stabilize the surface energy, which results in the microfaceted reconstructions. The formation of various nanostructures and the surface stoichiometric changes are discussed.

The morphological and structural characteristics of nanostructure rutile TiO2 were investigated by using x-ray diffraction, scanning electron microscopy, electron diffraction, conventional and high resolution transmission electron microscopy. As a product of the precursor template of hydrogen titanate nanofibers, rutile could exhibit forms like tree, sheaf, or bundle. Both the branch and trunk of tree-like rutile have the same growth axis of [001]. The sheaf-like rutile forms while it grows along both [001] and [] directions. The bundle-like rutile grows along only one [001] direction. Tree-like morphology of nanocrystals rutile is revealed to be controlled by (101) twin structure. Twin formation is a possible mechanism to decrease the density of defects and reduce the system energy as the crystal grows.

In principle, compositional profiling of the near-rim region of minerals can provide insight into cooling rates, but presumes that loss or gain of material from the crystal rim is not kinetically restricted. Trace element depth profiles collected for Zr, Hf, Ta, Nb, and U in amphibolite-facies rutile grains of the Catalina Schist, southern California, show significant variability within a single rock: Profiles of the same element among different grains can have significantly different slopes, grains with indistinguishable Zr profiles show vastly different Nb profiles, and grains with indistinguishable Nb profiles show different Zr profiles. Textural and kinetic idiosyncrasies within the matrix apparently affect the ability of specific crystals to accept or release trace elements, and impugn the common assumption that mineral surfaces maintain equilibrium at amphibolite-facies conditions. A new model that limits the flux of Zr from rutile grains helps explain commonly observed compositional profiles, and implies that inversion of compositional profiles assuming equilibrium among grain surfaces will invariably overestimate cooling rates. Few grains may record the low closure temperatures that experimentally determined diffusivities imply. Rather, higher temperatures will be retained, depending on the proximity of reactants and products in the matrix. Silicon diffusion does not control Zr reequilibration in rutile, and relative diffusion coefficients ( D's) of trace elements in rutile are D Zr ~ D Hf ~ 10 D Nb ~ 20 D Ta ~ 40 D U.

This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From an experimental perspective, a method was used to synthesize thulium-doped TiO2 nanoparticles in which Tm(3+) replaces Ti(4+) in the lattice, which to our knowledge has neither been reported nor studied theoretically so far. Different proportions of anatase and rutile phases were obtained at different annealing temperatures, and XRD and Raman spectroscopy also revealed the presence of a pyrochlore phase (Tm2Ti2O7) at 1173 K. Thus, the structure of the Tm-doped nanoparticles was thermally-controlled. Furthermore, XPS showed the presence of Tm(3+) in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm(3+) in the samples led to changes in the UV-Vis absorption spectra, so they showed photoluminescence properties and new states in the band gap, which produce a new lower energy electronic transition than the main TiO2 one. Periodic DFT calculations were performed to understand the experimentally produced structures. The production of oxygen vacancies was analysed and the changes generated in the structure were fully detailed. The DOS and PDOS analyses confirmed the experimental results obtained using UV-Vis spectroscopy, and showed that the new electronic states in the band gap are due to interactions of the f state of Tm and the p state of O. Likewise, the charge study and the ELF analysis indicate that when Tm is introduced into the TiO2 structure, the Ti-O bond around the oxygen vacancy is strengthened. Finally, an example of a photocatalytic application was developed to show the high efficiency of the samples due to the heterojunction in the interfaces of the phases in the samples, which improved the charge separation and the good charge carrier mobility due to the presence of the pyrochlore phase, as was also shown theoretically.

Rutile is a relatively common accessory phase in many geological environments, and although it is almost always composed dominantly of TiO2, it is also associated with a wide range of minor and trace element substitutions. The most prominent minor elements that occur in rutile are Fe, Cr, V, Nb and Ta. Like Ti, the latter two elements are essentially immobile in most non-magmatic metallic ore deposits, and their concentrations in rutile are largely influenced by precursor mineral compositions. Iron, Cr and V concentrations vary considerably in rutile hosted by ore deposits, and reflect combinations of precursor mineral composition and the bulk chemistry of the local mineralized or altered rock environment. However, in hydrothermal alteration zones, rutile compositions are clearly anomalous compared to those in unaltered host rocks, and have distinctive elemental associations and substitutions in different types of ore deposits. We have evaluated the mineral chemistry of rutile in >40 ore deposits worldwide. In general, rutile in volcanogenic massive sulfide deposits contains Sn (and locally W, Sb and/or Cu). Rutile from mesothermal and related gold deposits invariably contains W, and in some of the larger and more important deposits, also contains Sb and/or V. Tungsten-bearing detrital rutile grains from the Witwatersrand suggest that paleoplacer mineralization may have had a mesothermal/orogenic gold source. In some magmatic-hydrothermal Pd-Ni-Cu deposits, rutile contains Ni and Cu. Rutile associated with granite-related Sn deposits has strongly elevated concentrations of Sn and W, and granite-pegmatite W-Sn deposits contain rutile with these elements plus Nb and Ta. The Olympic Dam deposit hosts rutile that is enriched in W, Sn and Cu. Rutile associated with porphyry and skarn Cu and Cu-Au deposits tends to contain elevated W, Cu (and sometimes V). Although many ore deposits have well-defined and diagnostic rutile compositions, there are some compositional

The relative stability of TiO2 in the rutile and anatase structure is wrongly described by density functional theory in various local, semilocal, or even hybrid functional approximations. In this work, we have found that by considering high-order correlations in the adiabatic connection fluctuation-dissipation theory with the random phase approximation (ACFDT-RPA), rutile is correctly predicted to be more stable than anatase, which can be physically attributed to different characters in the electronic band structure of rutile and anatase, including, in particular, that rutile has a smaller band gap than anatase. We further consider the zero-point energy and finite-temperature effects based on the harmonic approximation, and we found that the inclusion of the zero-point energy correction can further increase the relative stability of rutile, and leads to a better quantitative agreement with available experimental measurements. Our study indicates the importance of considering high-order dynamical correlation effects to correctly predict the relative phase stability of polymorphic materials, especially for those systems in which the less stable phase as predicted by conventional local, semilocal or even hybrid density functional approximations has a smaller band gap than the more stable one.

A series of V2O5/TiO2 catalysts with different ratios of TiO2 rutile phase was prepared. Focusing on the effect of TiO2 rutile phase on V2O5/TiO2 catalyst for the selective catalytic reduction (SCR) of NO with NH3, the NO conversion for the different catalysts was investigated. The experimental results showed that a small amount of TiO2 rutile phase could improve the NO conversion significantly below 270 °C. Analysis by XRD, NH3-TPD, UV-vis, EPR and DFT calculation showed that the rutile phase of TiO2 supporter decreased the band gap, especially, the conduction band level. It improved the formation of reduced V species and superoxide ions that were important to the low-temperature SCR reaction.

Rutile is a common accessory mineral in igneous and high-grade metamorphic rocks and igneous, with many applications in geosciences. Rutile geochemistry, especially the high field strength elements (i.e., Nb and Ta), monitors many geological processes including subduction-zone metamorphism, while Zr provides temperature information in buffering assemblages. Rutile can also be used for U-Pb geochronology, but typically low U concentrations can make age dating difficult. Many applications of rutile now rely on laser ablation ICPMS (LA-ICPMS) analysis, a major disadvantage of this technique is the lack of reliable rutile standards. Here, we present laser ablation data of several rutile megacrysts from around the world, illustrating typical geochemical characteristics of potential standards. Whole-grain transects and depth profiles were collected on several rutiles, including Graves Mountain, Kragerø, Madagascar, Mozambique, Quebec, and Diamantina. Most transects, particularly across Graves Mountain and Diamantina, show dramatic zoning in Zr (up to 100 ppm), U (up to 10 ppm), and Nb (up to 1000 ppm). Rutile grains from Mozambique and Kragerø show little variation in concentration in Zr, U, and Nb. However, U concentrations generally range from 1ppm (Graves Mountain) to 45ppm (Kragero). Depth profiles (30-80s analysis; 15-40 μm) showed a combination of slight surface contamination plus minor to significant near-rim zoning. Some samples, such as Mozambique, show minor concentration changes in Zr, Nb, and Ta over the outer 10 μm but are otherwise unzoned, whereas U concentrations decrease for 25 μm then are constant. Kragero shows depth zoning throughout for Zr, Ta, and U but Nb is unzoned. Some rutile megacrysts show promise as standards (e.g. Mozambique and Kragero), but must be prepared to eliminate crystal surfaces. Other megacrysts would have to be subsampled within specific crystals to isolate chemical homogeneous domains.

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3 11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (110) rutile surface (Zhang et al., 2004b). TheMDsimulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3-11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 °C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (1 1 0) rutile surface (Zhang et al., 2004b). The MD simulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models

The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nbmore » and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr

The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio

The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 °C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at ∼300 °C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 °C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log DZr ∼10-25 m2/s at 650 °C and ∼10-30 m2/s at 250 °C) with diffusion length-scales of <0.2 μm in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change

The Magnet Cove Rutile Company mine was mapped by the U.S. Geological Survey in November 1944. The pits are on the northern edge of Magnet Cove and have been excavated in the oxidized zone of highly weathered and altered volcanic agglomerate. The agglomerate is composed of altered mafic igneous rocks in a matrix of white to gray clay, a highly altered tuff. The agglomerate appears layered and is composed of tuffaceous clay material below and igneous blocks above. The agglomerate is cut by aplite and lamprophyre dikes. Alkalic syenite dikes crop out on the ridge north of the pits. At the present stage of mine development the rutile seems to be concentrated in a narrow zone beneath the igneous blocks of the agglomerate. Rutile, associated with calcite and pyrite, occurs as disseminated acicular crystals and discontinuous vein-like masses in the altered tuff. Thin veins of rutile locally penetrate the mafic igneous blocks of the agglomerate.

TiO{sub 2} is a harmful impurity in the digestion of producing alumina. TiO{sub 2} in bauxite usually exists in the forms of rutile, anatase and brookite. In this paper, the authors studied the reaction of rutile in sodium aluminate liquor, examined the effects of OH{sup {minus}} ion concentration, adding amount of CaO and temperature on the reaction, achieved the kinetics equation and calculated the activation energy of the reaction.

This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From an experimental perspective, a method was used to synthesize thulium-doped TiO2 nanoparticles in which Tm3+ replaces Ti4+ in the lattice, which to our knowledge has neither been reported nor studied theoretically so far. Different proportions of anatase and rutile phases were obtained at different annealing temperatures, and XRD and Raman spectroscopy also revealed the presence of a pyrochlore phase (Tm2Ti2O7) at 1173 K. Thus, the structure of the Tm-doped nanoparticles was thermally-controlled. Furthermore, XPS showed the presence of Tm3+ in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm3+ in the samples led to changes in the UV-Vis absorption spectra, so they showed photoluminescence properties and new states in the band gap, which produce a new lower energy electronic transition than the main TiO2 one. Periodic DFT calculations were performed to understand the experimentally produced structures. The production of oxygen vacancies was analysed and the changes generated in the structure were fully detailed. The DOS and PDOS analyses confirmed the experimental results obtained using UV-Vis spectroscopy, and showed that the new electronic states in the band gap are due to interactions of the f state of Tm and the p state of O. Likewise, the charge study and the ELF analysis indicate that when Tm is introduced into the TiO2 structure, the Ti-O bond around the oxygen vacancy is strengthened. Finally, an example of a photocatalytic application was developed to show the high efficiency of the samples due to the heterojunction in the interfaces of the phases in the samples, which improved the charge separation and the good charge carrier mobility due to the presence of the pyrochlore phase, as was also shown theoretically.This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From

Mineral surfaces may have facilitated the concentration and polymerization of simple biomolecules into macromolecules while promoting the development of biochirality. In this study, rutile and aspartic acid (Asp) were investigated as a possible system in this scenario. Batch adsorption experiments were performed to examine the adsorption of Asp as a function of total concentration and pH. A constant background electrolyte of 0.1 M NaCl was applied to the system, and all solutions were purged with argon gas to eliminate carbon dioxide contamination. Asp adsorbs onto rutile to the highest extent over the pH range 3-5.5 suggesting that an acidic environment is required for the adsorption between Asp and rutile to occur in significant amounts. This pH range of maximum adsorption is constrained between the isoelectric point of Asp and the point of zero charge of rutile, which indicates that electrostatic effects are influencing Asp adsorption. Both the L- and D- enantiomers of Asp were individually adsorbed onto the rutile surface to determine the potential of the system for chiral selection. Preliminary results indicate that D-Asp may possibly adsorb in greater amounts than L-Asp at higher Asp total concentrations. This trend is unexpected as the growth planes dominating the rutile are achiral, and a more thorough study is required to validate this difference in adsorption. Nevertheless, this result may provide insight on the emergence of chiral selection in macromolecules within what might be a predominantly achiral prebiotic system.

Titanite and rutile are a common mineral pair in eclogites, and many equilibria involving these phases are potentially useful in estimating pressures of metamorphism. We have reversed one such reaction, {Mathematical expression} using a piston-cylinder apparatus. Titanite+kyanite is the high-pressure assemblage and our results locate the equilibrium between 15.5 15.9, 17.7-17.9, 18.8-19.0, and 20.0-20.2 kb at 900, 1000, 1050, and 1100??C, respectively. The experiments require a positive dP/dT of between 20.5 and 23.5 bars/??C for the reaction. We use the reversed equilibrium and two other reactions, {Mathematical expression} and {Mathematical expression} to calculate metamorphic conditions for three eclogite localities. Using these reactions in conjunction with garnet-clinopyroxene Fe2+-Mg exchange equilibria, conditions of metamorphism were 16 kb and 750??C for kyaniteeclogites from Glenelg, Scotland, 21 kb and 625??C for eclogite-facies mica schists from the Tauern Window, Austria, and 46 kb and 850??C for eclogite-facies biotite gneisses from the Kokchetav Massif, USSR. For the Scottish and Austrian eclogites, the pressures derived from the titanite-rutile reactions provide additional constraints on pressures for these localities, leading to precise estimates of metamorphic conditions. In the case of the Soviet Union eclogites, the results show that the silicate-oxide assemblage is consistent with the remarkable occurrence of diamond inclusions in the garnets. The results of this study suggest that titanite and rutile stably coexist in many eclogites and that titanite solid solutions are ideal or nearly so. ?? 1991 Springer-Verlag.

Hydrogen-related defects play crucial roles in determining physical properties of their host oxides. In this work, we report our systematic experimental and theoretical (based on density functional theory) studies of the defect states formed in hydrogenated-rutile TiO2 in gaseous H2 and atomic H. In gas-hydrogenated TiO2, the incorporated hydrogen tends to occupy the oxygen vacancy site and negatively charged. The incorporated hydrogen takes the interstitial position in atom-hydrogenated TiO2, forming a weak O-H bond with the closest oxygen ion, and becomes positive. Both states of hydrogen affect the electronic structure of TiO2 mainly through changes of Ti 3d and O 2p states instead of the direct contributions of hydrogen. The resulted electronic structures of the hydrogenated TiO2 are manifested in modifications of the electrical and optical properties that will be useful for the design of new materials capable for green energy economy. PMID:26627134

Vanadium dioxide (VO2) undergoing reversible metal-insulator phase transition could allow for the formation of an efficient thermochromic material for smart windows. However, solar radiation shielding performance is determined by transparent rutile VO2 filters, and the puzzling metal-insulator transition mechanism makes it challenging to explain the origin of the coexistence of strong near infrared absorption with high optical transparency. The band structure, the density of states, and the optical properties of rutile VO2 were calculated using the first-principles calculations. The calculated results of the structural and optical properties are in good agreement with the previously reported experimental findings. The calculated dielectric functions, electron energy-loss function and solar radiation shielding performance of the rutile VO2 filters indicate that rutile VO2 is a promising near-infrared absorption/reflectance material with the near-infrared radiation insulating abilities and a visible light transmittance. These properties arise from plasma oscillation and a collective oscillation (volume plasmons) of carrier electrons.

The surface science of titanium dioxide, TiO2, has attracted great amount of attention due to its high profile applications. This dissertation shows the development of well-controlled rutile (110) surfaces that provide a platform for studying the chemical and photochemical reactivity of rutile in technologically relevant environments, including air and solutions. Near-perfect rutile (110) surfaces characterized by atomically flat terraces and straight steps were produced using basic peroxide solutions. The reaction produced straight steps with a different orientation, different structure, and different reactivity from those prepared in ultrahigh vacuum. The morphology was explained by a site-specific model of rutile (110) etching based on metal oxo coordination chemistry. This work shows that one of the important roles of peroxo ligands in etching and growth reactions is to destabilize neighboring bonds and increase their lability. The peroxo ligands add a degree of reversibility to the growth reaction, leading to the formation of well-ordered crystals. In addition, this near-perfect rutile (110) surface is an ideal starting point for studying surface chemistry of rutile in technologically relevant environments. Under ambient conditions atmospheric CO2 reacted with adsorbed H2O and produced a self-assembled monolayer of HCO 3 on rutile (110) surfaces. The monolayer was formed on the near-perfect rutile surfaces prepared by basic peroxide etching, indicating that surface defects, such as Ti interstitials and O vacancies, were not required. DFT calculations suggested that the nanoscale water film adsorbed on the surface solvated the adsorbates and changed the reaction energetics. The HCO 3 monolayer was very stable, even in vacuum, which was a result of the strong bidentate bonding of HCO3. The formation of the strongly bound bicarbonate monolayer suggests that HCO3, instead of CO 2, plays a key role in the photoreduction of CO2. A high-quality, self

The synthesis of pure rutile titanium dioxide is not an easy achievement, as the crystallization process generally leads to mixtures of two or even three phases; moreover the synthetic processes normally used by industry require harsh reaction conditions. We carried out the synthesis of titanium dioxide from an aqueous titanium tetrachloride solution under microwave irradiation in the reaction time range of 5-120 min. We mostly obtained mixtures of rutile and anatase, but obtained single-phase rutile after a 2-h treatment at 160 deg. C; transmission electron micrographs revealed well-dispersed spherical nanoparticles. We also investigated the effects of dilution and addition of a dispersant (polyvinylpyrrolidone) on phase crystallization and particle shape.

In this communication, TiO2 nanocrystalline thin films synthesized by a room temperature (27 degrees C) chemical dip process. To our knowledge, this is first report of the preparation of nanoscale rutile TiO2 particles from common inorganic salt at such low temperature. Interestingly, unprecedented dynamic color change accompanies with titanium dioxide grain size, which can be seen with the naked eye that generated curiosity in our mind to check UV-vis absorption, where significant changes were observed. The room temperature synthesized thin films of rutile titanium dioxide make it a potential candidate for high-compatibility material, which can be used in artificial heart valves.

The adsorption of Nd 3+ onto rutile surfaces was examined by potentiometric titration from 25 to 250°C, in 0.03 and 0.30 m NaCl background electrolyte. Experimental results show that Nd 3+ sorbs strongly, even at low temperature, with adsorption commencing below the pH znpc of rutile. In addition, there is a systematic increase in Nd 3+ adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd 3+ on rutile. The primary mode of Nd 3+ adsorption was assumed to be the tetradentate configuration found for Y 3+ adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent "terminal" and two adjacent "bridging" surface oxygen atoms. Similarly, the adsorption of Na + counterions was also assumed to be tetradentate, as supported by MD simulations of Na + interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb + adsorption on rutile. Fitting parameters for Nd 3+ adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.

The adsorption of Nd{sup 3+} onto rutile surfaces was examined by potentiometric titration from 25 to 250 C, in 0.03 and 0.30m NaCl background electrolyte. Experimental results show that Nd{sup 3+} sorbs strongly, even at low temperature, with adsorption commencing below the pHznpc of rutile. In addition, there is a systematic increase in Nd{sup 3+} adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd{sup 3+} on rutile. The primary mode of Nd{sup 3+} adsorption was assumed to be the tetradentate configuration found for Y{sup 3+} adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent ''terminal'' and two adjacent ''bridging'' surface oxygen atoms. Similarly, the adsorption of Na{sup +} counterions was also assumed to be tetradentate, as supported by MD simulations of Na{sup +} interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb{sup +} adsorption on rutile. Fitting parameters for Nd{sup 3+} adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.

Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner

Super critical fluid is known as a suitable solvent in the dissolution and extraction process, due to its extreme high solubility and reactivity. On the other hand, further experimental approaches using supercritical fluid would offer new insights, especially in the field of novel material synthesis and crystal growth. We here report on the successful growth of single crystals with the rutile-type structure (MO2; M = Ti, Si, Ge and Sn) in the supercritical fluids (water or oxygen) by using laser heated diamond-anvil cell at above 5 GPa. The resultant product showed the rectangular hollow tube with several tens of microns in length and the wall thickness of less than 500 nm. TEM analyses demonstrated that this rectangular hollow tube single crystal is surrounded by the (110) face and grown along the [001] direction. The preferential growth of (110) face is consistent with the lowest surface energy of (110) in the rutile-type structure. In addition, the rapid cooling rate of LHDAC and the high-solubility of oxides into the supercritical fluids also play an important role for the formation of the rectangular hollow tube. The details of the experiments will be discussed in the presentation.

This work presents an experimental study on the specific quantitative contributions of antireflective and effective surface areas on the photocatalytic and antibacterial properties of rutile TiO{sub 2} nanospikes. They are studied when continuously distributed over the whole surface and when integrated into well-defined microstructures. The nanospikes were produced following MeV ion beam irradiation of bulk rutile TiO{sub 2} single crystals and subsequent chemical etching. The ion beam irradiation generated embedded isolated crystalline nanoparticles inside an etchable amorphous TiO{sub 2} layer, and nanospikes fixed to the not etchable TiO{sub 2} bulk substrate. The produced nanospikes are shown to resist towards aggressive chemical environments and act as an efficient UV antireflective surface. The photocatalytic activity experiments were performed under the ISO 10678:2010 protocol. The photonic and quantum efficiency are reported for the studied samples. The combined micro- and nanostructured surface triples the photonic efficiency compared to the initial flat surface. Results also revealed that the antireflective effect, due to the nanostructuring, is the dominating factor compared to the increase of surface area, for the observed photocatalytic response. The obtained results may be taken as a general strategy to design and precisely evaluate photoactive nanostructures.

A previously unknown resistive memory effect is reported in rutile titanium dioxide. Two Pt electrodes were placed on the surface of a rutile crystal, and a large voltage was applied between them. Afterwards, the device allowed current to pass in the direction of the voltage, but not in the other direction. The orientation of this rectification could then be switched by applying a large voltage of opposite sign. The effect was observed with electrodes on the (100) or (110) surfaces, but not the (001) surface. A plausible explanation is the field-induced motion of oxygen vacancies, which the large voltage might cause to pile up under the negative electrode, eliminating a Schottky barrier at that interface, but leaving a Schottky at the positive electrode intact. Parallels are drawn to other memory effects in titanium dioxide.

First-principle calculations are carried out to study the diffusion of Li ions in rutile structure RuO{sub 2}, a material for positive electrodes in rechargeable Li ion batteries. The calculations focus on migration pathways and energy barriers for diffusion in Li-poor and Li-rich phases using the Nudged Elastic Band Method. Diffusion coefficients estimated based on calculated energy barriers are in good agreement with experimental values reported in the literature. The results confirm the anisotropic nature of diffusion of Li ions in one-dimensional c channels along the [001] crystalline direction of rutile RuO{sub 2} and show that Li diffusion in the Li-poor phase is faster than in the Li-rich phase. The findings of fast Li diffusion and feasible Li insertion at low temperatures in the host rutile RuO{sub 2} suggest this material is a good ionic conductor for Li transport. The finding also suggests possible means for enhancing the performance of RuO{sub 2}-based electrode materials.

The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 1972 launched four decades of intensive research into the underlying chemical and physical processes involved. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. ). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.

Supercritical fluids with compositions intermediate between H2O and silicate are widely invoked as important transport agents in subduction zones. This proposal is in part motivated by the expectation that such fluids might have greater ability to dissolve and transport key trace elements at high P and T. As a test of this hypothesis, we measured the solubility of rutile (TiO2) in supercritical albite (ab, NaAlSi3O8)-H2O at 900°C, 1.5 GPa, from Xab = 0 to 0.3. At this P and T, rutile has very low solubility in H2O and there is full miscibility between H2O and ab melt. Experiments were conducted in a piston-cylinder apparatus with NaCl-graphite furnaces. In each, a 1.6 mm OD Pt inner capsule with a synthetic rutile crystal was lightly crimped and placed in a 3.5 OD Pt capsule with ultra pure H2O and powdered Amelia albite. Equilibrium was achieved after 4 hrs. Solubility was determined by the weight loss of the rutile grain. Quench textures consistent with supercritical behavior were observed in all runs. Residual corundum is present in the H2O-rich runs, but it decreases with increasing ab concentration. Results show that rutile solubility initially rises sharply with increasing ab concentration from 38 ppm in pure H2O to 739 ppm at Xab =0.05 (44 wt%). With further increase in ab, rutile solubility increases only slightly, to 922 ppm at Xab =0.25 (83 wt%). No significant solubility increase was noted near the critical compositon (~50 wt% ab). Our results show that intermediate fluids do not significantly enhance Ti solubility above dilute silicate-bearing solutions. The presence of residual Al2O3 and the sharp initial rise in rutile solubility at low Xab imply that, by analogy with silicate melts, Ti is present in solution as Na-Ti-O complexes (e.g., Dickenson and Hess, 1985, GCA, 49, 2289). However, the lack of residual corundum at high Xab suggests a transiton to different Ti species, perhaps aqueous NaAlSi3O8-like complexes. Our results give insight into rutile

We report a novel method of synthesizing rutile TiO2 nanocrystals at low temperature (200 degrees C) via a butanol rinsing process followed by heat treatment in an O2 atmosphere. The rutile nanocrystals show uniform size distribution of approximately 20 nm and good crystallinity confirmed by X-ray diffraction and transmission electron microscopy. A mechanism for the low temperature synthesis of rutile nanocrystals is rationalized in terms of an explosive thermal decomposition reaction of butoxy groups on TiO2 powders with O2 gas. Characterizations of the photovoltaic and photocatalytic properties of rutile nanocrystals exhibited higher photoactivity than large-sized conventional rutile powder, which demonstrates that this novel synthesis technology could expand applications of rutile powders to various photoactive devices beyond solar cells and photocatalysts.

The ability to accurately constrain the secular record of high- and ultra-high pressure metamorphism on Earth is potentially hampered as these rocks are metastable and prone to retrogression, particularly during exhumation. Rutile is among the most widespread and best preserved minerals in high- and ultra-high pressure rocks and a hitherto untested approach is to use mineral inclusions within rutile to record such conditions. In this study, rutiles from three different high- and ultrahigh-pressure massifs have been investigated for inclusions. Rutile is shown to contain inclusions of high-pressure minerals such as omphacite, garnet and high silica phengite, as well as diagnostic ultrahigh-pressure minerals, including the first reported occurrence of exceptionally preserved monomineralic coesite in rutile from the Dora-Maira massif. Chemical comparison of inclusion and matrix phases show that inclusions generally represent peak metamorphic assemblages; although rare prograde phases such as titanite, omphacite and corundum have also been identified implying that rutile grows continuously during prograde burial and traps mineralogic evidence of this evolution. Pressure estimates obtained from mineral inclusions, when used in conjunction with Zr-in-rutile thermometry, can provide additional constraints on the metamorphic conditions of the host rock. This study demonstrates that rutile is an excellent repository for high- and ultra-high pressure minerals and that the study of mineral inclusions in rutile may profoundly change the way we investigate and recover evidence of such events in both detrital populations and partially retrogressed samples.

The microscopic origin of magnetic birefringence in the rutile-type antiferromagnets XF2 (X=Mn, Fe, Co, or Ni) is analyzed on the basis of the theory of structural birefringence developed by Ewald and Born. The general principles of the Ewald-Born theory are reviewed. The magnetic birefringence can be explained by a small exchange-induced internal displacement of the fluorine atoms. Predictions from theory are compared with accurate crystal-structure analyses based on γ-ray-diffraction data. The agreement found between theory and experiment is excellent.

Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed.

The objective of this work is to develop and optimize the new dye-sensitized solar cell technology. In view of the infancy of rutile material development for solar cells, the PV response of the dye-sensitized rutile-based solar cell is remarkably close to that of the anatase-based cell.

Spectroscopic ellipsometry in the mid-infrared and far-infrared spectral range and generalized ellipsometry in the mid-infrared spectral range are used to investigate the anisotropic dielectric response of rutile TiO2. The ordinary and extraordinary dielectric function tensor components and all infrared active phonon mode parameters of single crystalline rutile TiO2 are determined with high accuracy for wavelengths from 3 μm to 83 μm. The data were acquired from samples of (001), (100), and (111) surfaces cut from bulk single crystals. A factorized model dielectric function is employed in order to determine the frequencies and damping parameters of the transverse and longitudinal phonon modes with A2u and Eu symmetries. The bands of total reflection of s- and p-polarized light in dependence of the angle of incidence for highly symmetric sample cuts and orientations are derived. Excellent agreement with phonon modes reported in literature is obtained. Introduction of two additional modes for ordinary as well as extraordinary component of the dielectric function tensor was necessary to most accurately match the experimental data. The spectral position of the additional modes is compared to the calculated phonon density of states. The low-frequency dielectric constants are calculated from the determined phonon mode parameters and the high-frequency dielectric constants by applying the Lyddanne-Sachs-Teller relation. The presented data revise existing infrared optical function data and will be suitable for interpretation of any kind of infrared spectra for bulk TiO2 single crystal substrates, thin films, and TiO2 nanostructures.

Ab initio calculations combined with tight-binding modelling have been performed in 5d-electron-based perovskite multilayers in the large spin-orbit coupling limit. The topological properties of the systems (SrTiO3)7/(SrIrO3)2andisoelectronic(KTaO3)7/(KPtO3)2 grown along the (111) direction have been analyzed as a function of on-site Coulomb repulsion U, parity asymmetry and uniaxial strain. The former is found to be a topological semimetal and the latter is a topological insulator describable as the high-U limit of the other one. This high-U phase can be driven to a trivial insulating phase by a perpendicular external electric field. In the talk, we will describe how to proceed in a similar way with rutile-based multilayered structures, where a 4d/5d electron dioxide with rutile structure, sandwiched by a band insulator like TiO2 or SnO2 can lead to topologically non-trivial properties if band filling and strain are tuned. We discuss also the possibility of obtaining similar topological states using isoelectronic fluorides. The electronic structure and properties of free-standing thin films will be also briefly discussed. We acknowledge support through the Ramon y Cajal Program and Xunta de Galicia through project no. EM2013/037.

In a photoelectrochemical (PEC) cell for water splitting, the critical issue is charge separation and transport, which is usually completed by designing semiconductor heterojunctions. TiO2 anatase-rutile mixed junctions could largely improve photocatalytic properties, but impairs PEC water splitting performance. We designed and prepared two types of TiO2 heterostructures with the anatase thin film and rutile nanowire phases organized in different sequences. The two types of heterostructures were used as PEC photoanodes for water splitting and demonstrated completely opposite results. Rutile nanowires on anatase film demonstrated enhanced photocurrent density and onset potential, whereas strong negative performance was obtained from anatase film on rutile nanowire structures. The mechanism was investigated by photoresponse, light absorption and reflectance, and electrochemical impedance spectra. This work revealed the significant role of phase sequence in performance gain of anatase-rutile TiO2 heterostructured PEC photoanodes.

We have grown TiO2 anatase films with rutile nanocrystalline inclusions using molecular beam epitaxy under different growth conditions. This model system is important for investigating the role of rutile/anatase interfaces in heterogeneous photocatalysis. To control the film structure, we grew a pure anatase (001) layer at a slow rate and then increased the growth rate to drive the nucleation of rutile particles. Structure analysis indicates that the rutile phase has four preferred orientations in the anatase film.

The trace element signatures of arc magmas are characterized by HFSE depletion relative to the LILE. Rutile, a common accessory phase in high-pressure assemblages, is an important reservoir for the HFSE and is often invoked to explain the HFSE depletion of arc magmas. This model is in part based on experimental studies, which show that rutile has very low solubility in pure H2O. However, rutile is also a common accessory to eclogite-facies vein assemblages of albite, paragonite and quartz, which likely precipitated from slab-derived fluids. This observation requires either that fluid fluxes were unrealistically high, or that current estimates of Ti solubility are too low. A possible solution to this problem is that dissolved silicate components can enhance Ti solubility via complexing. To test this, we measured the solubility of rutile in H2O-NaAlSi3O8 (albite) bearing fluids at high T and P. Experiments were conducted using a piston-cylinder apparatus with NaCl-graphite furnaces. A single synthetic rutile crystal was loaded into a 1.6 mm OD Pt inner capsule, which was lightly crimped and then placed in a 3.5 OD Pt outer capsule with ultra pure H2O and powdered Amelia albite. Solubility was determined by the weight loss of the rutile grain after 10 hrs. A time series demonstrates that equilibrium is achieved after 8-10 hrs. Preliminary results at 800°C, 1.0 GPa, show that rutile solubility rises with increasing NaAlSi3O8 concentration from 1.15(12) millimolal at 2.18 wt% NaAlSi3O8 to 3.77(13) at 8.80 wt% NaAlSi3O8. Corundum mats + fluid are observed in 3.4-8.80 wt% NaAlSi3O8 and are interpreted to be the result of incongruent dissolution of albite. Quenched melt spheres where observed in an experiment containing ~15 wt% NaAlSi3O8, but not at 8.80 wt%. At 8.80 wt% NaAlSi3O8, rutile solubility is higher by a factor of 6 relative to that in pure H2O. Our results suggest that TiO2 solubility is increased by complexing with Na-Al-Si-bearing fluid components. It has

Oriented rutile/hematite intergrowths from Mwinilunga in Zambia were investigated by electron microscopy methods in order to resolve the complex sequence of topotaxial reactions. The specimens are composed of up to several-centimeter-large euhedral hematite crystals covered by epitaxially grown reticulated rutile networks. Following a top-down analytical approach, the samples were studied from their macroscopic crystallographic features down to subnanometer-scale analysis of phase compositions and occurring interfaces. Already, a simple morphological analysis indicates that rutile and hematite are met near the orientation relationship. However, a more detailed structural analysis of rutile/hematite interfaces using electron diffraction and high-resolution transmission electron microscopy (HRTEM) has shown that the actual relationship between the rutile and hosting hematite is in fact . The intergrowth is dictated by the formation of equilibrium interfaces leading to 12 possible directions of rutile exsolution within a hematite matrix and 144 different incidences between the intergrown rutile crystals. Analyzing the potential rutile-rutile interfaces, these could be classified into four classes: (1) non-crystallographic contacts at 60° and 120°, (2) {101} twins with incidence angles of 114.44° and their complementaries at 65.56°, (3) {301} twins at 54.44° with complementaries at 125.56° and (4) low-angle tilt boundaries at 174.44° and 5.56°. Except for non-crystallographic contacts, all other rutile-rutile interfaces were confirmed in Mwinilunga samples. Using a HRTEM and high-angle annular dark-field scanning TEM methods combined with energy-dispersive X-ray spectroscopy, we identified remnants of ilmenite lamellae in the vicinity of rutile exsolutions, which were an important indication of the high-T formation of the primary ferrian-ilmenite crystals. Another type of exsolution process was observed in rutile crystals, where hematite precipitates

In northwest Turkey, ophiolitic meta-gabbros are exposed on the Kazdağ Massif located in the southern part of the Biga Peninsula. Trace element composition of rutile and Zr-in-rutile temperatures were determined for meta-gabbros from the Kazdağ Massif. The Zr content of all rutiles range from 176 to 428 ppm and rutile grains usually have a homogeneous Zr distribution. The rutile grains from studied samples in the Kazdağ Massif are dominated by subchondritic Nb/Ta (11-19) and Zr/Hf ratios (20-33). Nb/Ta and Zr/Hf show positive correlation, which is probably produced by silicate fractionation. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents. The core of rutile grains are generally characterized by low Nb/Ta ratios of 17-18 whereas the rims exhibit relatively high Nb/Ta ratios of 19-23. Trace element analyses in rutile suggest that these rutile grains were grown from metamorphic fluids. The P-T conditions of meta-gabbros were estimated by both Fe-Mg exchange and Zr-in-rutile thermometers, as well as by the Grt-Hb-Plg-Q geothermobarometer. The temperature range of 639 to 662 °C calculated at 9 kbar using the Zr-in-rutile thermometer is comparable with temperature estimates of the Fe-Mg exchange thermometer, which records amphibolite-facies metamorphism of intermediate P-T conditions. The P-T conditions of meta-ophiolitic rocks suggest that they occur as a different separate higher-pressure tectonic slice in the Kazdağ metamorphic sequence. Amphibolite-facies metamorphism resulted from northward subduction of the İzmir-Ankara branch of the Neo-Tethyan Ocean under the Sakarya Zone. Metamorphism was followed by internal imbrication of the Kazdağ metamorphic sequence resulting from southerly directed compression during the collision.

Electron spin resonance studies have been made on Verneuil-grown rutile single crystals, which were doped with a variety of transition gorup ions. Measurements were made at 9 GHz, both before and after UV irradiation, at temperatures in the range from 4.2 to 300 K. UV irradiation had two effects: (a) to affect the relative intensities of esr lines due to species already present, (b) to generate new esr spectra. Both effects are interpreted as representing a redistribution of charge amongst trapping centres. Seven UV generated centres have been identified and characterised in terms of their spin Hamiltonian parameters. Isochronal annealing techniques have been used to determine the ionisation temperatures of the traps. Observation of interactions and charge transfers between centres during isochronal annealing was used to determine the polarity and type of each centre.

Oxygen vacancy-vacancy interactions in rutile Ti O2 are studied in conjunction with polaron formation trends using density functional theory calculations. It is found that polarons strongly enhance the formation of oxygen vacancies in this material and also mediate the interactions between existing vacancies. At distances below 1 nm, two isolated and charge-neutral vacancies exhibit attractive interactions with an equilibrium distance of about 4 Å. The attractive forces between vacancies partly arise from the polaronic transfer of excess electrons to reduce the potential energy. These discoveries provide microscopic explanations to the vacancy clustering phenomena, as well as a practical approach to stabilize the polarons at arbitrary Ti atoms in Ti O2 .

We study the relation between hydrogen bonding and the vibrational frequency spectra of water on the (110) surface of rutile (α-TiO2) with three structural layers of adsorbed water. Using ab-initio molecular dynamics simulations at 280, 300 and 320K, we find strong, crystallographically-controlled adsorption sites, in general agreement with synchrotron X-ray and classical MD simulations. We demonstrate that these sites are produced by strong hydrogen bonds formed between the surface oxygen atoms and sorbed water molecules. The strength of these bonds is manifested by substantial broadening of the stretching mode vibrational band. The overall vibrational spectrum obtained from our simulations is in good agreement with inelastic neutron scattering experiments. We correlate the vibrational spectrum with different bonds at the surface in order to transform these vibrational measurements into a spectroscopy of surface interactions.

Rutile titania (TiO2) coatings have superior mechanical properties and excellent stability that make them preferential candidates for various applications. In order to prevent infection arising from bacteria, significant efforts have been focused on antibacterial TiO2 coatings. In the study, titania-nanosilver (TiO2/Ag) coatings with five different kinds of weight percentages of silver nanoparticles (AgNPs) were prepared by plasma spray. The feedstock powders, which had a composition of rutile TiO2 powders containing 1-10,000 ppm AgNPs, were double sintered and deposited on stainless steel substrates with optimized spraying parameters. X-Ray diffraction and scanning electron microscopy were used to analysize the phase composition and surface morphology of TiO2/Ag powders and coatings. Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were employed to examine the antibacterial activity of the as-prepared coatings by bacterial counting method. The results showed that silver existed homogeneously in the TiO2/Ag coatings and no crystalline changed happened in the TiO2 structure. The reduction ratios on the TiO2/Ag coatings with 10 ppm AgNPs were as high as 94.8% and 95.6% for E. coli and S. aureus, respectively, and the TiO2/Ag coatings with 100-1000 ppm AgNPs exhibited 100% bactericidal activity against E. coli and S. aureus, which indicated the TiO2/Ag coatings with more than 10 ppm AgNPs had strong antibacterial activity. Moreover, the main factors influencing the antibacterial properties of TiO2/Ag coatings were discussed with grain size and the content of silver as well as the microstructure of the coatings.

Natural rutile from China was found to have good photocatalytic activity for methylene blue (MB). Under UV irradiation, 50% of MB was decomposed in three hours by natural rutile, 90% in 77 hours and 100% in 119 hours. The Brunauer-Emmett-Teller (BET) specific surface area of natural rutile was only 0.4495 m2/g. In order to explain the decomposition of MB, rutile was characterized by XRD, FESEM and TEM, revealing a modulated structure. Crystal structural parameters are consistent with the data from JCPDS. Chemical composition approximates to Ti1.019O2. Photocatalytic properties of rutile are believed to relate to metal ionic substitution, vacancies and defects in its microstructure. Natural rutile is a practical photocatalyst, although its reaction rate is a fifth of anatase. Rutile might be effective and practical for a large-scale photocatalytic decomposition of organic pollutants in quiet and still waters (e.g. pools and lakes) since it is relatively cheap and widely available.

The paper deals with application of three nanomaterial systems: undoped TiO2, chromium-doped TiO2:Cr and TiO2-SnO2 synthesized by flame spray synthesis (FSS) technique for hydrogen sensing. The emphasis is put on the role of anatase and rutile polymorphic forms of TiO2 in enhancing sensitivity towards reducing gases. Anatase-to-rutile transformation is achieved by annealing of undoped TiO2 in air at 700 °C, specific Cr doping and modification with SnO2. Undoped TiO2 and TiO2-SnO2 exhibit n-type behaviour and while TiO2: 5 at.% Cr is a p-type semiconductor. X-ray diffraction (XRD) has been applied to determine anatase-to-rutile weight ratio as well as anatase and rutile crystal size. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to characterize the structure and morphological parameters. Optical reflectometry enabled to find and compare the band gaps E g of anatase and rutile predominated compositions. Electrical properties, i.e. the electrical conductivity and values of constant phase element (CPE), have been established on the basis of impedance spectroscopy. Dynamic responses of the electrical resistance as a function of hydrogen concentration revealed that predominance of rutile in anatase/rutile mixture is beneficial for gas sensing. Partial transformation to rutile in all three material systems under study resulted in an increased sensitivity towards hydrogen. It is proposed that this effect can be explained in a similar way as in photocatalysis, i.e. by specific band alignment and electron transfer from rutile to anatase to facilitate oxygen preadsorption on the surface of anatase grains.

The dynamical behavior of photoexcited states of TiO2 governs the activities of TiO2-based solar cells and photocatalysts. We determined the lifetimes of photoexcited electrons and holes in rutile and anatase TiO2 single crystals by combining advantages of time-resolved photoluminescence, photoconductance, and transient absorption spectroscopy. Electrons and holes in rutile show exponential decays with the lifetime of a few tens of nanoseconds, while non-exponential decays are observed in anatase, indicating the presence of multiple carrier trapping processes. We revealed the generic features of the carrier recombination processes in rutile and anatase TiO2.

Disseminated rutile and major amounts of topaz have been identified in Precambrian topaz-quartz gneiss northwest of Evergreen, Colo. The rutile occurs in quartz-topaz-sillimanite gneiss that forms a stratigraphic unit which is 11 to 100 feet thick and is identified along strike for more than 7,000 feet. Three composite chip samples taken across this unit contain 2.2 to 4.2 percent of rutile, by weight, in grains averaging from 0.1 to 0.3 millimeter in size. The topaz content, by weight, in the same samples ranges from 23 to 67 percent.

While rutile (TiO2) occurs in the heavy mineral suite of detrital sediments and originates mainly in medium- to high-grade metamorphic and some igneous rocks, there are very few applications of U-Pb dating of rutile to provenance studies; this is due to an overreliance on zircon, low U content of rutile limiting measurement quality by in situ methods, a higher proportion of common Pb relative to zircon, and a lack of widely available good quality reference materials. We have addressed these issues and characterized two ~ 1.8 Ga rutile reference materials by SEM, trace elements, U-Pb ID-TIMS, and intra-grain and inter-grain U-Pb LA-MC-ICP-MS analysis using mixed faraday and multiple ion counting detectors with high sensitivity. We have assessed U-Pb discordance and in situ variations in relative common Pb and age and their bearing on the quality of the reference materials for in situ U-Pb dating. The rutiles (Sugluk-4 and PCA-S207) come from granulite facies belts of the Canadian Shield, namely the northern Cape Smith Belt of Quebec and the Snowbird Tectonic Zone (Sasatchewan). The ID-TIMS data are slightly discordant due to variable common Pb and limited Pb loss; the variation in 6 single grains of Sugluk-4, that we use as the primary reference material, is <1% in 206Pb/238U, and <2% for 207Pb/206Pb (95 % conf.); after common Pb correction these variations are <1%. The measured variations are smaller than in existing reference materials (i.e. R10) in current use. LA-ICP-MC-MS data (n ~ 500 for each) have a reproducibility of 206Pb/238U and 207Pb/206Pb of ~2-4% (at the 2S level), which is only modestly worse than long-term data for multiple zircon standards, this being due to the real variation in measured values arising from limited Pb loss, age variation, and common Pb variability [1]. We have applied our refined method to the provenance of rutile from drainages from British Columbia, Bhutan, and the Brahmaputra River of NE India (predominant rutile ages ~ 50, 15

TiO2 microparticles are widely used in food products, where they are added as a white food colouring agent. This food additive contains a significant amount of nanoscale particles; still the impact of TiO2 nanoparticles (TiO2-NPs) on gut cells is poorly documented. Our study aimed at evaluating the impact of rutile and anatase TiO2-NPs on the main functions of enterocytes, i.e. nutrient absorption driven by solute-liquid carriers (SLC transporters) and protection against other xenobiotics driven by efflux pumps from the ATP-binding cassette (ABC) family. We show that acute exposure of Caco-2 cells to both anatase (12 nm) and rutile (20 nm) TiO2-NPs induce early upregulation of a battery of efflux pumps and nutrient transporters. In addition they cause overproduction of reactive oxygen species and misbalance redox repair systems, without inducing cell mortality or DNA damage. Taken together, these data suggest that TiO2-NPs may increase the functionality of gut epithelial cells, particularly their property to form a protective barrier against exogenous toxicants and to absorb nutrients.TiO2 microparticles are widely used in food products, where they are added as a white food colouring agent. This food additive contains a significant amount of nanoscale particles; still the impact of TiO2 nanoparticles (TiO2-NPs) on gut cells is poorly documented. Our study aimed at evaluating the impact of rutile and anatase TiO2-NPs on the main functions of enterocytes, i.e. nutrient absorption driven by solute-liquid carriers (SLC transporters) and protection against other xenobiotics driven by efflux pumps from the ATP-binding cassette (ABC) family. We show that acute exposure of Caco-2 cells to both anatase (12 nm) and rutile (20 nm) TiO2-NPs induce early upregulation of a battery of efflux pumps and nutrient transporters. In addition they cause overproduction of reactive oxygen species and misbalance redox repair systems, without inducing cell mortality or DNA damage. Taken

The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 A of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 degrees C that agrees quantitatively with the experimentally determined value (5.4+/-0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees C into quantitative agreement with the experimental value (4.8+/-0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength

The detailed solvation structure at the (110) surface of rutile ({alpha}-TiO{sub 2}) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 {angstrom} of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 C that agrees quantitatively with the experimentally determined value (5.4 {+-} 0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pH{sub znpc} values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pH{sub znpc} value of the rutile (110) surface at 25 C into quantitative agreement with the experimental value (4.8 {+-} 0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic

The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. In addition, rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects,more » band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.« less

Hedgehog-like mesoporous rutile TiO2 (HLR-TiO2) composed of well-defined nanoneedles is fabricated in a solvothermal system containing tetrabutyl titanate, hydrochloric acid aqueous solution and diethylene glycol with a proper volume ratio. A possible formation mechanism of the HLR-TiO2 is proposed on the basis of different experimental results and three different morphologies are obtained by changing the solvent with other conditions unchanged. Given its unique hierarchical mesoporous nanostructures, the HLR-TiO2 shows superior lithium storage properties with excellent discharge specific capacity of 243.3 mA h g-1 obtained after 100 cycles at a current rate of 1 C among the three samples, which is almost unparalleled to other rutile TiO2-based electrodes. In particular, a specific capacity of 80.2 mA h g-1 is still maintained after 2000 cycles even at a high current rate of 20 C, indicating that great potential of HLR-TiO2 as an electrode material for lithium-ion batteries (LIBs).

Nanocrystalline TiO2 powders of the rutile polymorph, synthesized by a sol-gel method, were treated with water solutions containing, respectively, formic, acetic, and citric acid and glycine in order to study the adsorption properties of these organic species. The samples were characterized by FTIR, Raman, powder XRD, and TEM. It was found that HCOOH, CH3COOH and HOC(COOH)(CH2COOH)2--but not NH2CH2COOH--adsorbed onto TiO2. The adsorption of HCOOH, CH3COOH and NH2CH2COOH onto the (110) surface of rutile was also studied by quantum-chemical periodic density functional theory (DFT) calculations. The organic molecules were from the computations found to adsorb strongly to the surfaces in a bridge-coordinating mode, where the two oxygens of the deprotonated carboxylic acid bind to two surface titanium ions. Surface relaxation is found to influence adsorption geometries and energies significantly. The results from DFT calculations and ab initio molecular-dynamics simulations of formic acid adsorption onto TiO2 are compared and match well with the experimental IR measurements, supporting the bridge-binding geometry of carboxylic-acid adsorption on the TiO2 nanoparticles.

The results of study of rutile inclusions in pyrope from the Internatsionalnaya kimberlite pipe are presented. Rutile is characterized by unusually high contents of impurities (up to 25 wt %). The presence of Cr2O3 (up to 9.75 wt %) and Nb2O5 (up to 15.57 wt %) are most typical. Rutile inclusions often occur in assemblage with Ti-rich oxides: picroilmenite and crichtonite group minerals. The Cr-pyropes with inclusions of rutile, picroilmenite, and crichtonite group minerals were formed in the lithospheric mantle beneath the Mirnyi field during their joint crystallization from melts enriched in Fe, Ti, and other incompatible elements as a result of metasomatic enrichment of the depleted lithospheric mantle.

Vertically aligned rutile TiO2 nanowire arrays (NWAs) with lengths of ∼44 μm have been successfully synthesized on transparent, conductive fluorine-doped tin oxide (FTO) glass by a facile one-step solvothermal method. The length and wire-to-wire distance of NWAs can be controlled by adjusting the ethanol content in the reaction solution. By employing optimized rutile TiO2 NWAs for dye-sensitized solar cells (DSCs), a remarkable power conversion efficiency (PCE) of 8.9% is achieved. Moreover, in combination with a light-scattering layer, the performance of a rutile TiO2 NWAs based DSC can be further enhanced, reaching an impressive PCE of 9.6%, which is the highest efficiency for rutile TiO2 NWA based DSCs so far.

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Atomistic simulations reveal that ceria nanorods, under uniaxial tension, can accommodate over 6% elastic deformation. Moreover, a reversible fluorite-to-rutile phase change occurs above 6% strain for a ceria nanorod that extends along [110]. We also observe that during unloading the stress increases with decreasing strain as the rutile reverts back to fluorite. Ceria nanorods may find possible application as vehicles for elastic energy storage.

This article describes a facile approach to the synthesis of rutile nanostructures in the form of porous fibers or bundles of nanotubes by maneuvering the surface wettability of yarns made of polystyrene nanofibrils. Specifically, hierarchically porous fibers were obtained by hydrolyzing titanium tetraisopropoxide to form TiO2 nanoparticles in the void spaces among hydrophobic nanofibrils in each yarn. After calcination in air at 800 °C, the resultant fibers were comprised of many interconnected rutile nanoparticles whose diameters were in the range of 20–80 nm. After converting the nanofibrils and yarns into hydrophilic surfaces through plasma treatment, however, the TiO2 formed conformal coatings on the surfaces of nanofibrils in each yarn during hydrolysis instead of just filling the void spaces among the nanofibrils. As a result, bundles of rutile nanotubes were obtained after the sample had been calcined in air at 800 °C. The thermodynamically stable rutile nanostructures were then explored as supports for Pt nanoparticles whose catalytic activity was evaluated using the reduction of p-nitrophenol by NaBH4. The Pt supported on porous rutile fibers exhibited a better performance than the Pt on rutile nanotubes in terms of both induction time (tind) and apparent rate constant (kapp). PMID:23763369

A novel multiple step growth (MSG) process has been developed to synthesize rutile nanorods (NRs) on fluorine-doped tin oxide (FTO) glass with the assistance of a self-assembled monolayer (SAM) aiming to increase the internal surface area of the 1D materials for dye sensitized solar cell (DSSC) applications. The experimental result reveals that the SAM layer can be selectively decomposed at the tip of the nanorod, namely the rutile (001) surface, due to the anisotropic photocatalytic property of the rutile. The remaining SAM layer on the side-wall of the NRs remains intact and serves as water repellent which prevents the radial growth of the NRs during the next step hydrothermal synthesis; therefore, the spacing between the NRs and the porosity of the NR array can be retained after additional growth cycles. On the other hand, introduction of a middle layer formed via TiCl4 solution treatment before the next growth cycle is found to be an effective way to control the diameters of the newly grown NRs. The performance of DSSC made from the rutile NRs grown using the MSG technique has been examined, and it is significantly affected by the internal surfaces of the NRs. Furthermore, the MSG combined with NR etching treatment by acid at low temperature (150 °C) leads to a significant enhancement in the solar cell performance. The gigantic wettability difference of the NRs before and after the SAM treatment as well as the MSG method could be adapted to prepare superhydrophobic and superhydrophilic nanostructured patterns for other applications.

Dirac points in two-dimensional electronic structures are a source for topological electronic states due to the ±π Berry phase that they sustain. Here we show that two rutile multilayers [namely (WO2)2/(ZrO2)n and (PtO2)2/(ZrO2)n ], where an active bilayer is sandwiched by a thick enough (n =6 is sufficient) band insulating substrate, show semimetallic Dirac dispersions with a total of four Dirac cones along the Γ -M direction. These become gapped upon the introduction of spin-orbit coupling, giving rise to an insulating ground state comprising four edge states. We discuss the origin of the lack of topological protection in terms of the valley spin-Chern numbers and the multiplicity of Dirac points. We show with a model Hamiltonian that mirror-symmetry breaking would be capable of creating a quantum phase transition to a strong topological insulator, with a single Kramers pair per edge.

Threshold displacement energies are determined for Ti and O in rutile TiO 2 using molecular dynamics simulations with an empirical model. The simulations involve the introduction of a primary knock-on atom (PKA) with a range of energies (30-150 eV) in various crystallographic directions at 160 K. We observe the formation of stable Frenkel defects, as well as defect recovery via low-energy interstitial migration mechanisms. The latter causes significant statistical variation between simulation outcomes, which leads to the definition of a defect formation probability. This probability is characterized as a function of PKA energy in order to define the threshold displacement energy and compare with experimental results. Using a probability of 10%, the average threshold displacement energy is around 40 eV for oxygen (comparable to experiment) and 105 eV for titanium. Using a probability of 50%, the values are 65 eV and 130 eV respectively, which may be more appropriate for use in TRIM calculations. In addition, we run a parallel set of calculations using a second empirical model, finding that the detailed results are highly model-dependent, particularly the oxygen defect structures and energies, which are compared to new ab initio data.

In this paper, pure rutile and anatase-rutile TiO2 nanoparticles have been successfully synthesised via a green route by hydrolysis of titanium tetrachloride with room temperature acidic ionic liquid 3-methyl-1-(3-sulfonylpropyl) imidazolium trifluoromethanesulfonate [HO3S(CH2)3MIM][CF3SO3] in aqueous medium. The influence of pH of the solution by varying molar ratio of substrate and ionic liquid has been investigated in both sol⿿gel and hydrothermal synthesis of TiO2 with significant variation in phase, phase composition (ratio of rutile to anatase) and morphology as indicated by various structural analysis such as XRD, TEM, BET, Raman and UV⿿vis absorption spectroscopy. The results indicate formation of a bunch of aligned thin flaky nano-rods of TiO2 which look like nano-flowers with a crystal size of 3⿿5 nm by sol⿿gel method, while in case of hydrothermal method well-defined rutile solid nanorods of TiO2 were formed with variable length in the range of 120⿿170 nm and 20⿿24 nm in width. The photocatalytic activity of the prepared TiO2 samples has been determined by the photodegradation of methyl orange dye (20 ppm) under UV light. Best photocatalytic activity was exhibited by sample S-2 prepared via sol⿿gel method.

The Zr-in-rutile geothermometer is potentially a widely applicable tool to estimate peak metamorphic temperatures in rocks from diverse geological settings. In order to evaluate its usefulness and reliability to record and preserve high temperatures in granulite facies rocks, rutile from UHT rocks was investigated to assess different mechanisms of Zr (re-)distribution following cooling from high temperature. Granulite facies paragneisses from the lowermost part of the Ivrea Zone, Italy, incorporated as thin sheets into the extensive basaltic body of the Mafic Complex were selected for this study. The results show that Zr-in-rutile thermometry, if properly applied, is well suited to identify and study UHT terranes as it preserves a record of temperatures up to 1190 °C, although the thermometer is susceptible to partial post-peak metamorphic resetting by Zr diffusion. Texturally homogeneous rutile grains preserve Zr concentrations corresponding to temperatures of prograde rutile growth. Diverse rutile textures and relationships between some rutile host grains and included or adjacent Zr-bearing phases bear testimony to varying mechanisms of partial redistribution and resetting of Zr in rutile during cooling and link Zr-in-rutile temperatures to different steps of the metamorphic evolution. Rutile grains that equilibrated their Zr concentrations at temperatures above 1070 °C (i.e. 1.1 wt% Zr) could not retain all Zr in the rutile structure during cooling and exsolved baddeleyite (ZrO2). By subsequent reaction of baddeleyite exsolution lamellae with SiO2, zircon needles formed before the system finally closed at 650-700 °C without significant net loss of Zr from the whole host rutile grain. By reintegration of zircon exsolution needles, peak metamorphic temperatures of up to 1190 °C are derived for the studied rocks, which demonstrates the suitability of this solution thermometer to record UHT conditions and also confirms the extraordinary geological setting of the

We have investigated the influence of the deposition variables on photocatalytic properties of epitaxial rutile films. Despite a large lattice misfit of rutile with sapphire substrate, (2 0 0) epitaxial layers were grown on (0 0 0 1)sapphire by domain matching epitaxy paradigm. Using {phi}-scan XRD and cross section TEM, the epitaxial relationship was determined to be rutile(1 0 0)||sapphire(0 0 0 1), rutile(0 0 1)||sapphire(1 0 -1 0), and rutile(0 1 0)||sapphire(1 -2 1 0). Based on the XRD patterns, increasing the repetition rate introduced tensile stress along the film normal direction, which may arise as a result of trapped defects. Formation of such defects was studied by UV-VIS, PL, and XPS techniques. AFM studies showed that the film roughness increases with the repetition rate. Finally, photocatalytic performance of the layers was investigated through measuring decomposition rate of 4-chlorophenol on the films surface. The films grown at higher frequencies revealed higher photocatalytic efficiency. This behavior was mainly related to formation of point defects which enhance the charge separation. - Graphical abstract: In this report, epitaxial rutile TiO{sub 2} thin films were deposited by PLD process under various deposition rates (frequencies) and their physical and chemical properties, especially photocatalytic performance, were investigated. It was found that photocatalytic efficiency improves when frequency increases. This behavior was mainly related to formation of point defects which enhance the charge separation. Highlights: Black-Right-Pointing-Pointer Rutile epitaxial thin films were deposited via PLD process under different frequencies. Black-Right-Pointing-Pointer Defect characteristic was studied. Black-Right-Pointing-Pointer Photocatalytic performance of the layers was investigated.

The g-factor formulas for V4+ and Cr5+ ions in the rutile-type crystals are deduced from Jahn-Teller effect and contributions of the charge transfer levels. The tetragonal distortions ΔR = -0.0045, -0.0045 and -0.0067 nm, and Δθ = 0°, -0.001° and 0°, for GeO2:V4+, TiO2:V4+ and TiO2:Cr5+, respectively. The calculations of the g-factors agree well with the experimental values. The contributions of the charge transfer levels to g factors increase with the increasing valence state. It must be taken into account in the precise calculations of g factors for the high valence state d1 ions in crystals.

Summary Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed. PMID:26199854

Titanium dioxide has been widely used as an efficient transition metal oxide photocatalyst. However, its photocatalytic activity is limited to the ultraviolet spectrum range due to the large bandgap beyond 3 eV. Efforts to reduce the bandgap to achieve a broader spectrum range of light absorption have been successfully attempted via the experimental synthesis of dopant-free metastable surface structures of rutile-type TiO2 (011) 2 × 1. This new surface phase possesses a reduced bandgap of ∼2.1 eV, showing great potential for an excellent photocatalyst covering a wide range of visible light. There is a need to establish the atomistic structure of this metastable surface to understand the physical cause for the bandgap reduction and to improve the future design of photocatalysts. Here, we report computational investigations in an effort to unravel this surface structure via swarm structure-searching simulations. The established structure adopts the anatase (101)-like structure model, where the topmost 2-fold O atoms form a quasi-hexagonal surface pattern and bond with the unsaturated 5-fold and 4-fold Ti atoms in the next layer. The predicted anatase (101)-like surface model can naturally explain the experimental observation of the STM images, the electronic bandgap, and the oxidation state of Ti(4+). Dangling bonds on the anatase (101)-like surface are abundant making it a superior photocatalyst. First-principles molecular dynamics simulations have supported the high photocatalytic activity by showing that water and formic acid molecules dissociate spontaneously on the anatase (101)-like surface.

The infrared spectra of hydrous, oriented single crystals of synthetic Al-doped and pure rutile were measured from room temperature to 1000 °C at 1 bar using a heating stage. At room temperature, the spectra show only one band at 3278 cm-1 in pure rutile, and two additional bands at 3303 and 3323 cm-1 in Al-doped rutile. The main band associated with Al at 3323 cm-1 loses intensity as temperature increases and nearly disappears already at 300 °C. This suggests that the corresponding defect only forms during cooling and, therefore, water speciation in rutile at room temperature is not representative of subduction zone or upper mantle conditions. All OH bands shift to lower wavenumbers at elevated temperatures with dν/dT = -0.0831 cm-1 K-1 for the main band at 3278 cm-1. This strong low-frequency shift is unexpected for an OH bond involved in hydrogen bonding, indicating decreasing O-O distance for the OH band. Together with the extreme broadening of the band at high temperature, it suggests some weakening of the OH bond strength and a rapid exchange of protons, consistent with rapid hydrogen diffusion in rutile.

Photoemission electron microscopy (PEEM) excited by x-ray and UV sources is used to investigate epitaxial anatase thin films embedded with rutile nanocrystals, a model system for the study of heterocatalysis on mixed-phase TiO2. Both excitation sources show distinct contrast between the two TiO2 phases, however, the contrast is reversed. Rutile nanocrystals appear darker than the anatase film in X-ray PEEM images but brighter in UV-PEEM images. Topography-induced contrast is dominant X-ray PEEM imaging, whereas work function contrast, dominates for UV-PEEM. Work function contrast results from the differences in work function and surface defect state densities between the two phases near the Fermi level. This assertion is confirmed by UPS data that shows the rutile work function to be 0.2 eV lower and a greater occupied valence band density-of-states in rutile (100) than in anatase (001). Since the boundaries between rutile nanocrystals and the anatase film are clearly resolved, these results indicate that PEEM studies of excited state dynamics and heterocatalysis are possible at chemically intriguing mixed-phase TiO2 interfaces and grain boundaries.

This work reports a theoretical x-ray absorption near-edge structure (XANES) spectroscopy study at the Ti K-edge in TiO(2) rutile. We present detailed ab initio computations of the Ti K-edge XANES spectrum performed within the multiple-scattering framework. An extensive discussion is presented concerning the size of the cluster needed to reproduce the experimental spectrum, especially regarding the split main absorption line. In addition, the role of the exchange and correlation potential (ECP) in reproducing all the experimental XANES features is discussed. The best agreement between experimental data and computations is obtained by using real ECP potentials, i.e. the energy-dependent Dirac-Hara exchange potential, or by using only the real part of the energy-dependent Hedin-Lundqvist complex potential, together with an additional imaginary constant to account for the core-hole lifetime and the experimental resolution. The addition of the imaginary part of the HL potential worsens the agreement between the experimental and calculated spectra, indicating the failure of the complex part of the Hedin-Lundqvist ECP in accounting for the electron damping in these systems.

The purpose of this SAND Report is to document efforts in the extraction and failure analyses of sleeve-style Lightning Arrestor Connectors (LACs). Several MC3080 and MC3079 LACs were recovered from the field and tested as part of the Enhanced Surveillance Campaign. A portion of these LACs failed retesting. Terry Ernest (01733), the LAC Component Engineer, provided eleven MC3080 LACs for evaluation where four of the LACs failed IR/DCW and one failed FRB requirements. The extraction of rutile sleeves from failed LACs was required to determine the source of failure. Rutile sleeves associated with connector function failures were examined for cracks, debris as well as any other anomalies which could have caused the LAC to not function properly. Sleeves that failed FRB or that experienced high FRB exhibited high symmetry, smooth surface, long-flow amicon, and slightly over-sized inside diameter. LACs that failed DCW or IR requirements had rutile sleeves that exhibited breakdown tracks.

We discuss the formation of TiO2 thin films via DC reactive magnetron sputtering. The oxygen concentration during sputtering proved to be a crucial parameter with respect to the final film structure and properties. The initial deposition provided amorphous films that crystallise upon annealing to anatase or rutile, depending on the initial sputtering conditions. Substoichiometric films (TiOx<2), obtained by sputtering at relatively low oxygen concentration, formed rutile upon annealing in air, whereas stoichiometric films formed anatase. This route therefore presents a formation route for rutile films via lower (<500 °C) temperature pathways. The dynamics of the annealing process were followed by in situ ellipsometry, showing the optical properties transformation. The final crystal structures were identified by XRD. The anatase film obtained by this deposition method displayed high carriers mobility as measured by time-resolved microwave conductance. This also confirms the high photocatalytic activity of the anatase films.

In this paper, a novel method of infiltration of TiO2 nanoparticles into the coating of the cellulose and rutile shielded metal arc welding electrode is shown. Tensile properties and strength of weld metals were correlated to the chemical composition of the weld metals, ferrite type, and non-metallic inclusion type, size and composition. As infiltration time is increased in the cellulose electrodes, the non-metallic inclusion count increases and their size decreases. They act as inoculants and lead to the replacement of Widmanstaetten with the finegrained acicular ferrite which increases the mechanical properties of the welds. The modification of rutile electrodes with low and medium infiltration time also refines the microstructure and increases the mechanical properties. Specimens welded with rutile electrodes infiltrated at maximum duration exhibited the lowest mechanical properties due to the relatively large non-metallic inclusions that act as void nucleation sites and the appearance of large grain allotriomorphic ferrite in the weld metal.

Nanostructure anatase and rutile type TiO2 were synthesized from dissolution roasted ilmenite from natural ilmenite sand as the starting materials. Anatase TiO2 and rutile TiO2 (high crystallinity) with the diameters of 20-100 nm were obtained by calcined soluble ilmenite sand produced by leaching process. Calcinations of the xerogel TiO2 from liquor products were conducted for 4 hours at temperature of 450 °C. The samples were characterized by XRD (X-ray diffraction), STA (simultant thermal analysis), TEM (Transmission Electron Microscopy), and BET surface area. Titania Anatase-Rutile form as a mixture were produced by titania slag with the hydrolysis product. While, in another route, complete titania anatase phase was produced through hydrolysis and condensation steps of leach liquors. This synthesis methods provide a simple route to fabricate nanostructure TiO2 from low cost material.

Nanostructure anatase and rutile type TiO{sub 2} were synthesized from dissolution roasted ilmenite from natural ilmenite sand as the starting materials. Anatase TiO{sub 2} and rutile TiO{sub 2} (high crystallinity) with the diameters of 20–100 nm were obtained by calcined soluble ilmenite sand produced by leaching process. Calcinations of the xerogel TiO{sub 2} from liquor products were conducted for 4 hours at temperature of 450 °C. The samples were characterized by XRD (X-ray diffraction), STA (simultant thermal analysis), TEM (Transmission Electron Microscopy), and BET surface area. Titania Anatase-Rutile form as a mixture were produced by titania slag with the hydrolysis product. While, in another route, complete titania anatase phase was produced through hydrolysis and condensation steps of leach liquors. This synthesis methods provide a simple route to fabricate nanostructure TiO{sub 2} from low cost material.

In general, anatase TiO2 exhibits higher photocatalytic activities than rutile TiO2. However, the reasons for the differences in photocatalytic activity between anatase and rutile are still being debated. In this work, the band structure, density of states, and effective mass of photogenerated charge carriers for anatase, rutile and brookite TiO2 are investigated by the first-principle density functional theory calculation. The results indicate that anatase appears to be an indirect band gap semiconductor, while rutile and brookite belong to the direct band gap semiconductor category. Indirect band gap anatase exhibits a longer lifetime of photoexcited electrons and holes than direct band gap rutile and brookite because the direct transitions of photogenerated electrons from the conduction band (CB) to valence band (VB) of anatase TiO2 is impossible. Furthermore, anatase has the lightest average effective mass of photogenerated electrons and holes as compared to rutile and brookite. The lightest effective mass suggests the fastest migration of photogenerated electrons and holes from the interior to surface of anatase TiO2 particle, thus resulting in the lowest recombination rate of photogenerated charge carriers within anatase TiO2. Therefore, it is not surprising that anatase usually shows a higher photocatalytic activity than rutile and brookite. This investigation will provide some new insight into understanding the difference of photocatalytic activity among anatase, rutile and brookite.

Hierarchical-structured nanotubular silica/titania hybrids incorporated with particle-size-controllable ultrafine rutile titania nanocrystallites were realized by deposition of ultrathin titania sandwiched silica gel films onto each nanofiber of natural cellulose substances (e.g., common commercial filter paper) and subsequent flame burning in air. The rapid flame burning transforms the initially amorphous titania into rutile phase titania, and the silica gel films suppress the crystallite growth of rutile titania, thereby achieving nano-precise size regulation of ultrafine rutile titania nanocrystallites densely embedded in the silica films of the nanotubes. The average diameters of these nanocrystallites are adjustable in a range of approximately 3.3-16.0 nm by a crystallite size increment rate of about 2.4 nm per titania deposition cycle. The silica films transfer the electrons activated by crystalline titania and generate catalytic reactive species at the outer surface. The size-tuned ultrafine rutile titania nanocrystallites distributed in the unique hierarchical networks significantly improve the photocatalytic performance of the rutile phase titania, thereby enabling a highly efficient photocatalytic degradation of the methylene blue dye under ultraviolet light irradiation, which is even superior to the pure anatase-titania-based materials. The facile stepwise size control of the rutile titania crystallites described here opens an effective pathway for the design and preparation of fine-nanostructured rutile phase titania materials to explore potential applications.

Concurrent Li-ion and electron conductivity in rutile and anatase TiO2 nanoparticles was studied using multiscale simulations. We show that charge transport in titania nanoparticles is determined by the competition of charge redistribution towards the particle boundaries and constant Li+ and electron fluxes. In nanoparticles smaller than the Debye length the constant flux prevails and the conductivity has a dual ionic and electronic character, while for larger nanoparticles conductivity becomes predominately ionic. Simulations revealed that the temperature dependence of Li-ion conductivity in anatase is very weak, while in rutile the conductivity decreases with temperature in small nanoparticles and increases in large nanoparticles.

CrCl2 and CrF2 with the distorted Rutile-type crystal structure are known to exhibit different antiferromagnetic (AF) structures at low temperatures. CrF2 has a simple N_eel structure in common with other uorides, whereas CrCl2 exhibits a characteristic layered AF structure. We provide a simple scenario to understand the emergence of such layered AF structure on the basis of an orbital degenerate double-exchange model on the Rutile-type structure lattice.

The widely used artificial nanoparticles (NPs) and the excess of ammonium (NH4(+)) fertilizers are easily released into the natural environment. So, clarifying the mobility of NPs in the presence of NH4(+) is therefore of great urgency and high priority. Currently, few studies focus on the transport and deposition of nanoparticle titanium dioxide (nTiO2) in single and binary systems containing NH4(+), especially describing this process by a mathematical model. In this work, the comparison between the transport and retention of rutile nTiO2 in single and binary electrolyte solutions of NH4Cl and/or NaCl (0.5-50 mM) were conducted at pH 6.0 and 8.0 through running the column experiments. Experimental results show that the aggregation and retention of nTiO2 in solution containing mono-valence cations obeys the order as follows: NH4(+) > Na(+) > Na(+) + NH4(+) at the same ion strength (IS). It is attributed to the lower critical coagulation concentration (CCC) of rutile nTiO2 in NH4(+) than that in Na(+) solution. In particular, the simultaneous presence of NH4(+) and Na(+) favors the transportability of nTiO2 due to the strong competitive adsorption on the surface of NPs. The two-site kinetic retention model provides the good simulation for their transport behavior. The likely mechanism is that the secondary energy minimum of nTiO2 in NH4(+) system associated with the greater K2 at surface Site 2 (from model) on sand can be explained for the more reversible deposition. Ammonium leachate associated with NPs can thus be considered a serious concern.

Rutile is a common accessory mineral that occurs in a wide spectrum of metamorphic rocks, such as in blueschists, eclogites, and granulites and as one of the most stable detrital heavy minerals in sedimentary rocks. The advent of rutile trace element thermometry has generated increased interest in a better understanding of rutile formation. This study documents important analytical advances in in situ LA-ICP-MS U/Pb geochronology of rutile: (1) Matrix matching, necessary for robust in situ dating is fulfilled by calibrating and testing several rutile standards (R10, R19, WH-1), including the presentation of new TIMS ages for the rutile standard R19 (489.5 ± 0.9 Ma; errors always stated as 2 s). (2) Initial common lead correction is routinely applied via 208Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb concordia ages for the two other rutile standards (493 ± 10 Ma for R19; 2640 ± 50 Ma for WH-1) and four rutile-bearing metamorphic rocks (181 ± 4 Ma for Ivrea metapelitic granulite; 339 ± 7 Ma for Saidenbach coesite eclogite; 386 ± 8 Ma for Fjortoft UHP metapelite; 606 ± 12 Ma for Andrelandia metepelitic granulite) always agree within 2% with the reported TIMS ages and other dating studies from the same localities. The power of in situ U/Pb rutile dating is illustrated by comparing ages of detrital rutile and zircon from a recent sediment from the Christie Domain of the Gawler Craton, Australia. While the U/Pb age spectrum from zircons show several pronounced peaks that are correlated with magmatic episodes, rutile U/Pb ages are marked by only one pronounced peak (at ca 1,675 Ma) interpreted to represent cooling ages of this part of the craton. Rutile thermometry of the same detrital grains indicates former granulite-facies conditions. The methods outlined in this paper should find wide application in studies

The local structures of the two rhombic Ni 3+ centers (on the substitutional and interstitial sites) in rutile (TiO 2) are theoretically studied from the perturbation formulas of the g factors for a 3d 7 ion of low spin (S = 1/2) in rhombically distorted octahedra. In these formulas, the contributions to the g factors from the low symmetrical parts of the crystal-fields as well as the spin-orbit coupling interaction and orbitals of the ligands are taken into account. From the investigations, the ligand octahedron in the substitutional Ni 3+ center may suffer a slightly larger axial elongation (characterized by the axial distortion angle Δ αs ≈ - 1.09°) than that (ΔαsH≈-0.73°) in the host and the much smaller perpendicular distortion (characterized by the rhombic distortion angle Δ θs ≈ - 0.75°) than that (ΔθsH≈-9.0°) in the host due to the Jahn-Teller effect. For the interstitial Ni 3+ center, the ligand octahedron is found to undergo a smaller compression (characterized by the axial distortion angle Δ αi ≈ 1.48°) than that (ΔαiH≈8.17°) in the host and a slighter rhombic distortion (Δ θi ≈ 0.1°) than that (ΔθiH≈7.0°) in the host due to the Jahn-Teller effect. The calculated g factors based on the above structural parameters show better agreement than those based on the host structural parameters and those in absence of the spin-orbit coupling and the orbitals of the ligands with the experimentally observed values.

The indentation microhardness of stoichiometric and reduced single crystal rutile (TiO2) from 25 to 800 C is presented in this paper. The results serve two main purposes. One is to assess the effect of rutile's stoichiometry on its hardness. The other is to test recently suggested theory on solid lubrication with sub Stoichiometric rutile in an effort to better understand shear controlled phenomenon. Microhardness was measured using a Vickers diamond indentor on both vacuum and hydrogen reduced single crystal rutile from 25 to 800 C. The results indicate that stoichiometry and temperature have a pronounced effect on rutile's hardness. The measured effects lend support to theory on solid lubrication by enhanced crystallographic slip and suggest that solid lubricant materials may be produced by careful atomic level tailoring (stoichiometry control).

In order to enhance the electron transport on the photoelectrodes of dye-sensitized solar cells, one-dimensional rutile nanorods were prepared using electrospun TiO2 nanofibers. The grain size of the nanorods increased with increasing temperature. Electrochemical impedance spectroscopy measurements revealed reduced interface resistance of the cells with the one-dimensional rutile nanorods due to the improved electron transport and the enhanced electrolyte penetration. Intensity-modulated photocurrent/photovoltage spectroscopy showed that the one-dimensional rutile nanorods provided the electrons with a moving pathway and suppressed the recombination of photogenerated electrons. However, an excessive quantity of rutile nanorods created an obstacle to the electrons moving in the TiO2 thin film. The photoelectrode with 7 wt.% rutile nanorods optimized the performance of the dye-sensitized solar cells. PMID:23331863

Shielded metal arc welding using covered electrodes is the most common welding process. Sometimes the covering contains naturally occurring radioactive materials (NORMs). In Spain the most used electrodes are those covered with rutile mixed with other materials. Rutile contains some detectable natural radionuclides, so it can be considered a NORM. This paper mainly focuses on the use of MCNP (Monte Carlo N-Particle Transport Code) as a predictive tool to obtain doses in a factory which produces this type of electrode and assess the radiological impact in a specific facility after estimating the internal dose.To do this, in the facility, areas of highest radiation and positions of workers were identified, radioactive content of rutile and rutile covered electrodes was measured, and, considering a worst possible scenario, external dose at working points has been calculated using MCNP. This procedure has been validated comparing the results obtained with those from a pressurised ionisation chamber and TLD dosimeters. The internal dose has been calculated using DCAL (dose and risk calculation). The doses range between 8.8 and 394 μSv yr(-1), always lower than the effective dose limit for the public, 1 mSv yr(-1). The highest dose corresponds to the mixing area.

Solar-light driven water splitting is a promising way for the sustainable production of molecular hydrogen, the latter representing an efficient carrier for energy storage and conversion into common liquid fuels. In search of novel catalysts for high-performance water splitting devices, Co-pyrphyrin (CoPy) has been recently synthesized and successfully used as a homogeneous water reduction catalyst. We investigate the adsorption of this molecule on the rutile TiO2(110) surface as a possible first step towards the design of a heterogeneous water reduction system. We find that the adsorption of the molecule is stabilized by the interaction of the cyano groups with the under-coordinated Ti centers present at the surface. This interaction induces the rehybridization of the molecular orbitals localized on the cyano groups and the realignment of the lowest unoccupied molecular states. Moreover, the highest occupied molecular orbital of CoPy@rutile(110) is localized on CoPy and the energy gap turns out to be significantly smaller than the gap of pristine rutile(110). This implies that direct or indirect injection of electrons from CoPy to the rutile(110) surface is in principle possible upon the absorption of light in the visible range. On the other hand, the electronic properties of the Co(ii) center are not modified by the adsorption, which suggests that CoPy and its derivatives may be used in water electrolysis for hydrogen production also in the adsorbed state.

Visible-light active photocatalysts were prepared by doping Cu-TiO2 through the sol-gel method. The influence of the preparation conditions such as pH of sol-gel solution and calcination temperature on the properties of TiO2-Cu was investigated. The presence of Cu caused reduction of band-gap energy, which was more visible in the rutile-type TiO2. Low pH of sol-gel solution such as pH 1.5 favorized formation of rutile during calcination and caused slower growth of the crystallites with increasing temperature of calcination in comparison with sol-gel prepared at pH 3. XPS measurements showed that Cu was placed mostly on the surface of TiO2. For sample calcined at 600 °C, the surface concentration of copper was 1.1 wt.%. The presence of both, rutile phase and Cu, increased adsorption of phenol and facilitated its photocatalytic decomposition. Moreover, reduced band-gap energy in rutile-type TiO2-Cu photocatalyst enabled phenol decomposition under visible light.

A new process of producing synthetic rutile from molten titanium slag with the addition B2O3 is proposed. The process includes a molten modification process and a leaching process. The molten modification process was conducted by adding B2O3 into molten slag. The leaching process was conducted by adding hydrochloric acid and subsequent NaOH. The results show that CaO and MgO are leached out by hydrochloric acid and that synthetic rutile is further improved by NaOH. The optimized conditions are 2% B2O3 amount, 5% hydrochloric concentration, 80°C leaching temperature, and 30 min leaching time. The synthetic rutile with 86.77% TiO2 and 1.23% (CaO + MgO) was prepared. From x-ray diffraction results, thermodynamic calculation and the theory of bond parameter function, with the addition of B2O3, calcium silicate is transformed into calcium borate and anosovite is transformed into magnesium borate. Calcium borate and magnesium borate are leached out by hydrochloric acid, leading to the enrichment of rutile.

The availability of low-index rutile TiO2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxialgrowth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO2(001) surfaces can be prepared with an atomically ordered reconstructedsurface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surface energy associated withmore » the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxialgrowth of TiO2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.« less

Review of some of the results of a reflection microscopy and electron microprobe study performed on a part of the Luna 20 soil sample designated as the East Coast Consortium aliquot. The study is restricted to analyses of the oxides of Fe, Ti, Mg, Mn, Cr, and Al in this sample. The spinel mineral group, ilmenite and rutile only are discussed.

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

The dynamical behavior of photoexcited states of TiO{sub 2} governs the activities of TiO{sub 2}-based solar cells and photocatalysts. We determined the lifetimes of photoexcited electrons and holes in rutile and anatase TiO{sub 2} single crystals by combining advantages of time-resolved photoluminescence, photoconductance, and transient absorption spectroscopy. Electrons and holes in rutile show exponential decays with the lifetime of a few tens of nanoseconds, while non-exponential decays are observed in anatase, indicating the presence of multiple carrier trapping processes. We revealed the generic features of the carrier recombination processes in rutile and anatase TiO{sub 2}.

Using the GW method within many-body perturbation theory, we investigate the electronic properties of the rutile (011) surfaces with different reconstruction patterns. We find that keeping the Ti:O ratio on the reconstructed surface to 1:2 enlarges the bandgap of the rutile (011) surface to ca. 4.0 eV. Increasing the content of O atoms in the surface can turn rutile into a semi-metal. For some surfaces, it is important to apply self-consistent GW calculation to get the correct charge distributions for the frontier orbitals, which are relevant to the photocatalytic behavior of TiO2.

All terminations of the (1x1) rutile (110), (101), (001), (100) and (111) surfaces are classified according to their electrostatic polarity. Six are found to be non-polar. The plane-wave density functional theory code CASTEP is used with a GGA-PBE exchange-correlation functional and a vacuum/material slab supercell method to calculate the surface energy density of symmetric thin rutile films with the six non-polar terminations in vacuum. The ratio of the surface energy densities of a rutile crystal with {111} and {110} facets in water is deduced using Lagrange multipliers and found to be consistent with the DFT vacuum results.

The premise of the Wilson et al. comment is that the Ti-in-quartz solubility calibration (Thomas et al. in Contrib Mineral Petrol 160:743-759, 2010) is fundamentally flawed. They reach this conclusion because P- T estimates using the Ti-in-quartz calibration differ from their previous interpretations for crystallization conditions of the Bishop and Oruanui rhyolites. If correct, this assertion has far-reaching implications, so a careful assessment of the Wilson et al. reasoning is warranted. Application of the Ti-in-quartz calibration as a thermobarometer in rutile-free rocks requires an estimation of TiO2 activity in the liquid ( a_{{{{TiO}}_{ 2} }} (liquid-rutile); referenced to rutile saturation) and an independent constraint on either P or T to obtain the crystallization temperature or pressure, respectively. The foundation of Wilson et al.'s argument is that temperature estimates obtained from Fe-Ti oxide thermometry accurately reflect crystallization conditions of quartz in the two rhyolites discussed. We maintain that our experimental approach is sound, the thermodynamic basis of the Ti-in-quartz calibration is fundamentally correct, and our experimental results are robust and reproducible. We suggest that the reason Wilson et al. obtain implausible pressure estimates is because estimates for T and a_{{{{TiO}}_{ 2} }} they used as input values for the Ti-in-quartz calibration are demonstrably too high. Numerous studies show that Fe-Ti oxide temperature estimates of some rhyolites are substantially higher than those predicted by well-constrained phase equilibria. In this reply, we show that when reasonable input values for T and a_{{{{TiO}}_{ 2} }} (liquid-rutile) are used, pressure estimates obtained from the Ti-in-quartz calibration are well aligned with phase equilibria and essentially identical to melt inclusion volatile saturation pressures.

In this paper, we employ state-of-the-art theoretical approaches to elucidate the structures of the (011) surface of rutile (R-)TiO2. An unexpectedly rich chemistry has been uncovered. Titanyl-TiO2 and titanyl-Ti2O3 reconstructions can be used for rationalizing the experimental findings, matching the STM images and the changes in the band gap. From the viewpoint of thermodynamics, the predicted MF(111)-TiO reconstruction is more reasonable than the previously proposed MF(111)-TiO3 model, although there is a structural similarity. The richness of surface phases, the formation of which is driven by thermodynamic conditions and surface stress release, implies the multifunctionality of the R-TiO2(011) surface. After the clarification of TiO2(011) and TiO2(110) surface structures {PRL, 2014, 113, 266101} (the most important surfaces of rutile), the origin of the Brønsted acidity of R-TiO2, which has remained a mystery at the atomic level, can also be addressed in the near future.

The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. Rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers

The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. In addition, rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.

The rutile TiO2(110) surface is the most studied surface of titania and considered as a prototype of transition metal oxide surfaces. Reactions on flat TiO2(110)-(1×1) surfaces are well studied, but the processes occurring on the step edges have barely been considered. Based on scanning tunneling microscopy studies, we here present experimental evidence for the existence of O vacancies along the ⟨11¯1⟩R step edges (OS vac.’s) on rutile TiO2(110). Both the distribution of bridging O vacancies on the terraces and temperature-programed reaction experiments of ethanol-covered TiO2(110) point to the existence of the OS vac.’s. Based on experiments and density functional theory calculations, we show that OS vac.’s are reactive sites for ethanol dissociation via O-H bond scission. Implications of these findings are discussed.

First principle calculations using density functional theory (DFT) and full-potential linearized augmented plane waves (FP-LAPW) method are performed to investigate the structural and electronic properties of rutile phase titanium, vanadium, ruthenium, iridium and tin dioxides, TiO2, VO2, RuO2, IrO2, and SnO2, respectively. The exchange correlation function is described using the local density approximation (LDA) and the generalized gradient approximation (GGA). The structural parameters of the dioxides are found to be in a fair agreement with experimental values and previous calculations. TiO2 exhibits the maximum cohesive energy and RuO2 exhibits the minimum, which is opposite to the trend of pure bulk metals. Titanium dioxide in the left of the periodic table exhibits an insulating behavior with an underestimated bandgap of 2 eV. As the d-band filling increases in VO2, the energy bands shift by 3 eV from those of TiO2 to cross the Fermi level and exhibit a metallic behavior with a pseudo gap to the right of the Fermi level. The energy bands coalescence in RuO2 and IrO2 exhibiting metallic behaviors. However, for a complete filled d-band SnO2, the insulating behavior is retrieved. The distortion of the octahedrons in the rutile structure lifts the degeneracy of the eg orbitals causing further splittings.

The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights.

The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights. PMID:26998188

The Gulf of Maine, an embayment of the New England margin, is floored by shallow, glacially scoured basins that are partly filled with late Pleistocene and Holocene silt and clay containing 0.7 to 1.0 wt percent TiO2 chiefly in the form of silt-size rutile. Much of the rutile in the Gulf of Maine mud probably formed diagenetically in poorly cemented Carboniferous and Triassic coarse-grained sedimentary rocks of Nova Scotia and New Brunswick after the dissolution of titanium-rich detrital minerals (ilmenite, ilmenomagnetite). The diagenesis of rutile in coarse sedimentary rocks (especially arkose and graywacke) followed by erosion, segregation, and deposition (and including recycling of fine-grained rutile from shales) can serve as a model for predicting and prospecting for unconsolidated deposits of fine-grained TiO2. -from Authors

In the present study, we probe into the phase transition from anatase to rutile in nanocrystalline thin films under thermal annealing and swift heavy ion (SHI) irradiation. TiO{sub 2} thin films were prepared through chemical route using sol-gel and spin coating techniques on silicon (100) substrates. The structural studies of the annealed films were characterized by GAXRD and Raman spectroscopy. Though thermal annealing is known to cause transformation from anatase to rutile phase of TiO{sub 2} in a temperature interval of 700 to 900 C, in nanoparticle thin films, we found {approx}35 vol% of anatase still remains even after annealing at 1000 C. SHI irradiation by 200 MeV Ag ions on the other hand resulted in complete conversion to rutile phase at fluence of 3x10{sup 12} ions.cm{sup -2}. SHI induced thermal spike seems to be responsible for conversion of anatase to rutile phase.

Rietveld powder X-ray diffraction analysis of the rutile films of titanium oxide prepared by pulsed laser deposition was carried out. The crystallite size increased with increase of substrate temperature, while the strain showed a reverse trend. The films synthesized at temperature {>=}573 K showed that the crystal structure was almost close to that of bulk rutile structure. The influence of the substrate temperature on the lattice parameters and oxygen coordinates were also studied in the present work.

The binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg{sup 2+}, Ca{sup 2+}, or Sr{sup 2+}) or monovalent (Na{sup +}, K{sup +}, or Rb{sup +}) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na{sup +} > K{sup +} > Rb{sup +} shows a 'reverse' lyotropic trend, while the divalent cations on the same surface exhibit a 'regular' lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr{sup 2+} > Ca{sup 2+} > Mg{sup 2+}). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO{sup -} group and the rutile, helping to 'trap' the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO{sup -} group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.

different gold-titania photocatalysts . Gold supported on a commercial anatase: rutile mixture has been found to be 3 times more active for hydrogen...production than the previously reported gold on anatase photocatalysts . Other products detected were ethene and acetaldehyde; these products were...ethanol and water-ethanol mixtures over a range of different gold- titania photocatalysts . Gold supported on a commercial anatase: rutile mixture has

We study terahertz photoconductivity of a rutile single crystal between 10 and 300 K under strong photoexcitation by femtosecond pulses at 266 nm. A marked dependence of the carrier mobility on the carrier density is observed leading to highly complex transport phenomena on a picosecond time scale. We develop a general model of carrier photoconductive response in the case of time dependent inhomogeneous distribution of carrier density and mobility. This allows us to assess an important role of both electrons and holes in the response of photoexcited rutile. At low temperatures, the carrier mobility is initially reduced due to the electron-hole scattering and increases by one order of magnitude upon ambipolar diffusion of the carriers into deeper regions of the sample. At room temperature, contributions of transient hot optical phonons and/or of midinfrared polaron excitations with charge-density-dependent dielectric strength emerge in the photoconductivity spectra.

Hydrogen donors in ZnO and rutile TiO2 are probed by means of photoconductivity and IR absorption. It is shown that the O-H bonds giving rise to the local vibrational modes (LVMs) of interstitial hydrogen at 3611 and 3290 cm-1 in the case of ZnO and TiO2, respectively, also occur in the photoconductivity spectra as Fano resonances. The effects of isotope substitution, concentration, sample thickness, influence of other donors present in both oxides are considered. Based on the shape and frequency of these resonances, it is concluded that the apparent ionization energy of interstitial hydrogen in rutile TiO2 is less than 300 meV. By a direct comparison, we also demonstrate that photoconductive detection of LVMs of defects in thin semiconductor films is superior to the standard IR absorption.

In nanostructured thin films, photogenerated charge carriers can access the surface more easily than in dense films and thus react more readily. However, the high surface area of these films has also been associated with enhanced recombination losses via surface states. We herein use transient absorption spectroscopy to compare the ultrafast charge carrier kinetics in dense and nanostructured TiO2 films for its two most widely used polymorphs: anatase and rutile. We find that nanostructuring does not enhance recombination rates on ultrafast time scales, indicating that surface state mediated recombination is not a key loss pathway for either TiO2 polymorph. Rutile shows faster, and less intensity-dependent recombination than anatase, which we assign to its higher doping density. For both polymorphs, we conclude that bulk rather than surface recombination is the primary determinant of charge carrier lifetime. PMID:27564137

A combined study of IR absorption, photoconductivity, photoluminescence and Raman measurements in ZnO samples supports the theoretical suggestions of a shallow bond-centered hydrogen donor and a shallow hydrogen donor within the oxygen vacancy. In rutile TiO2 we also identify a shallow hydrogen donor in contrast to recent theoretical predictions. A possible solution to this obvious discrepancy is proposed.

Different lengths of rutile TiO2 nanowires (NW) with wide-open space for effective material filling were used as photoanodes for perovskite solar cells. Cells with 900 nm nanowires as photoanodes exhibit a current density of 22 mA cm(-2) and an efficiency of 11.7%, outperforming the reported TiO2 nanowire-based perovskite solar cells.

The high pressure transformation of rutile to TiO{sub 2}-II with the α-PbO{sub 2} structure is known to be kinetically hindered. In this study we show that a hydrothermal environment at 6 GPa and 650 °C provides appreciable rates for producing single phase bulk samples of TiO{sub 2}-II. So obtained TiO{sub 2}-II was characterized by scanning electron microscopy, powder X-ray diffraction, Raman and Far-IR spectroscopy. The structural properties are identical to TiO{sub 2}-II from dry transitions. Transmission electron microscopy studies strongly indicate that Ostwald ripening processes play an important role in the hydrothermally assisted transformation and subsequent growth of TiO{sub 2}-II crystals. TiO{sub 2}-II is thermally stable to about 550 °C. At 600 °C the onset of the transformation to rutile is observed. The thermal expansion in the temperature range from room temperature to 500 °C is highly anisotropic, virtually affecting only the c unit cell parameter (α{sub c}=7.1(2)×10{sup −6} °C{sup −1}). The pressure–temperature conditions for the hydrothermally assisted transformation of rutile are viable for industrial production settings, and in light of the large technological significance of TiO{sub 2}, TiO{sub 2}-II may present an interesting target for large-scale synthesis. - Graphical abstract: Highly crystalline TiO{sub 2}-II, which is the high pressure form of titania with the α-PbO{sub 2} structure, can be prepared from rutile at 6 GPa and 650 °C when employing a hydrothermal environment. Display Omitted.

Hydroxyls are present as surface terminations of transition metal oxides under ambient conditions and may modify the properties of supported catalysts. We perform first-principles density functional theory calculations to investigate the role of hydroxyls on the catalytic activity of supported gold clusters on TiO{sub 2} (rutile). We find that they have a long-range effect increasing the adhesion of gold clusters on rutile. While hydroxyls make one gold atom more electronegative, a more complex charge-transfer scenario is observed on larger clusters which are important for catalytic applications. This enhances the molecular adsorption and coadsorption energies of CO and O{sub 2}, thereby increasing the catalytic activity of gold clusters for CO oxidation, consistent with reported experiments. Hydroxyls at the interface between gold and rutile surface are most important to this process, even when not directly bound to gold. As such, accurate models of catalytic processes on gold and other catalysts should include the effect of surface hydroxyls.

Highlights: ► Photocatalytic deactivation of Escherichia coli in presence of TiO{sub 2} nanoparticles ► The presence of catalyst is less important when the radiation is in the UV range ► Rutile has an higher efficiency respect to anatase under visible light. - Abstract: The photocatalytic deactivation of Escherichia coli HB101 by two different structures of TiO{sub 2}, rutile and anatase (used separately and in a 1:1 mixture), was examined. The microorganism was deposited on a filter membrane containing 520 mg/m{sup 2} of TiO{sub 2} and then irradiated by a neon lamp. In order to study the rate of deactivation of the microorganism we studied four different exposure times: 20, 40, 60 and 90 min. The results showed that rutile has an antimicrobial activity higher than anatase, while the mixture had values near to the average between them in every condition. The highest difference in the inactivation capacity of the two structures is observable at shorter times. The effect of the different crystal phases was evaluated by Scanning Electron Microscopy.

According to the HRTEM study, the UHP jadeite-quartzite mineral (Rutile, TiO(2)) in Anhui Province, Dabie Mountains, China, has ultrastructures such as 011 two-dimensional commensurable modulated structures or superstructures, [011] twin domain structures, dislocations and crystal deformations. The SAED patterns and HRTEM images indicate the existence of the deformations and stacking faults on the interface of [011] twin crystal of rutile and its two-dimensional commensurate modulated structures with repetition period 0.753 nm (3d(011)) has tetragonal symmetry, cell parameters a = 3a0 = 1.377 nm (a0 = 0.459 nm), c = c0 = 0.3 nm. The modulated structures of rutile were probably caused by the isomorphic replacement of Ti(4+) and position modulation or occupation modulation of oxygen atoms in different degree; the deformation structures reveal that during the process of crystallization and mineralization, this mineral may be affected by the geological environment (such as temperature, pressure and stress), metamorphism and deformation.

In this study, we present a combined density functional theory and many-body perturbation theory study on the electronic and optical properties of TiO(2) brookite as well as the tetragonal phases rutile and anatase. The electronic structure and linear optical response have been calculated from the Kohn-Sham band structure applying (semi)local as well as nonlocal screened hybrid exchange-correlation density functionals. Single-particle excitations are treated within the GW approximation for independent quasiparticles. For optical response calculations, two-particle excitations have been included by solving the Bethe-Salpeter equation for Coulomb correlated electron-hole pairs. On this methodological basis, gap data and optical spectra for the three major phases of TiO(2) are provided. The common characteristics of brookite with the rutile and anatase phases, which have been discussed more comprehensively in the literature, are highlighted. Furthermore, the comparison of the present calculations with measured optical response data of rutile indicate that discrepancies discussed in numerous earlier studies are due to the measurements rather than related to an insufficient theoretical description.

Nucleic acids, the storage molecules of genetic information, are composed of repeating polymers of ribonucleotides (in RNA) or deoxyribonucleotides (in DNA), which are themselves composed of a phosphate moiety, a sugar moiety, and a nitrogenous base. The interactions between these components and mineral surfaces are important because there is a tremendous flux of nucleic acids in the environment due to cell death and horizontal gene transfer. The adsorption of mono-, oligo-, and polynucleotides and their components on mineral surfaces may have been important for the origin of life. We have studied here interactions of nucleic acid components with rutile (TiO2), a mineral common in many terrestrial crustal rocks. Our results suggest roles for several nucleic acid functional groups (including sugar hydroxyl groups, the phosphate group, and extracyclic functional groups on the bases) in binding, in agreement with results obtained from studies of other minerals. In contrast with recent studies of nucleotide adsorption on ZnO, aluminum oxides, and hematite, our results suggest a different preferred orientation for the monomers on rutile surfaces. The conformations of the molecules bound to rutile surfaces appear to favor specific interactions, which in turn may allow identification of the most favorable mineral surfaces for nucleic acid adsorption.

Liu and co-workers [Phys. Rev. B 82, 161415 (2010)] discussed the long-standing debate regarding whether H2O molecules on the defect-free (110) surface of rutile ( -TiO2) sorb associatively, or there is dissociation of some or all first-layer water to produce hydroxyl surface sites. They conducted static density functional theory (DFT) and DFT molecular dynamics (DFT-MD) investigations using a range of cell configurations and functionals. We have reproduced their static DFT calculations of the influence of crystal slab thickness on water sorption energies. However, we disagree with several assertions made by these authors: (a) that second-layer water structuring and hydrogen bonding to surface oxygens and adsorbed water molecules are weak ; (b) that translational diffusion of water molecules in direct contact with the surface approaches that of bulk liquid water; and (c) that there is no dissociation of adsorbed water at this surface in contact with liquid water. These assertions directly contradict our publishedwork, which compared synchrotron x-ray crystal truncation rod, second harmonic generation, quasielastic neutron scattering, surface charge titration, and classical MD simulations of rutile (110) single-crystal surfaces and (110)-dominated powders in contact with bulk water, and (110)-dominated rutile nanoparticles with several monolayers of adsorbed water.

Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical (DFT) and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO2 is presented. Using the organic catechol on rutile TiO2(110) as a model system it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal by about ±27 in an alternating fashion. In the lowest-energy structure one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, while the other OH group forms a H-bond to the next catechol neighbor. Through proton exchange with the surface this structure transforms into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO2.

Titanium dioxide (TiO(2)), known to exhibit good biocompatibility, is applied in this study as a thin film formed onto polyetheretherketone (PEEK) substrate, which has been widely used in spinal interbody fusion cages. For successful deposition, an arc ionplating (AIP) technique was applied to deposit TiO(2) at low deposition temperature without damaging PEEK substrate, while providing satisfactory film adhesion. This study systematically investigates the effects of TiO(2) thin film phase composition and surface characteristics, controlled by using different target current and substrate bias, on osteoblast compatibility. Experimental results showed that anatase phase (A-TiO(2)) and/or rutile phase (R-TiO(2) ) TiO(2) coatings, respectively, can be prepared in appropriate deposition conditions. Overall, the TiO(2)-coated PEEK presented better osteoblast compatibility than the bare PEEK material in terms of cell adhesion, cell proliferation, and cell differentiation abilities, as well as osteogenesis performance (as determined by levels of osteopontin, osteocalcin, and calcium content). Surface roughness and hydrophilicity of the AIP-TiO(2) films were found to be responsible for significant osteoblast cell growth. It is also noticeable that the R-TiO(2) exhibited better osteoblast compatibility than the A-TiO(2) due to the presence of negatively charged hydroxyl groups on R-TiO(2) (110) surface in nature.

In this paper, we present the results of X-band EPR spectra of Co2+ ion doped rutile (TiO2) which is one of the most promising memristor material. We obtained the angular variation of spectra in three mutually perpendicular planes at liquid helium (7-13 K) temperatures. Since the impurity ions have ½ effective spin and 7/2 nuclear spin, a relatively simple spin Hamiltonian containing only electronic Zeeman and hyperfine terms was utilized. Two different methods were used in theoretical analysis. Firstly, a linear regression analysis of spectra based on perturbation theory was studied. However, this approach is not sufficient for analyzing Co+2 spectra and leads to complex eigenvectors for G and A tensors due to large anisotropy of eigenvalues. Therefore, all spectra were analyzed again with exact diagonalization of spin Hamiltonian and the high accuracy eigenvalues and eigenvectors of G and A tensors were obtained by taking into account the effect of small sample misalignment from the exact crystallographic planes due to experimental conditions. Our results show that eigen-axes of g and A tensors are parallel to crystallographic directions. Hence, our EPR experiments proves that Co2+ ions substitute for Ti4+ ions in lattice. The obtained principal values of g tensor are gx=2.110(6), gy=5.890(2), gz=3.725(7) and principal values of hyperfine tensor are Ax=42.4, Ay=152.7, Az=26 (in 10-4/cm).

We employ semilocal density functionals [local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and meta-GGAs)], LSDA plus Hubbard U (LSDA+U) theory, a nonlocal range-separated Heyd-Scuseria-Ernzerhof hybrid functional (HSE06), and the random-phase approximation (RPA) to assess their performances for the ground-state magnetism and electronic structure of a strongly correlated metal, rutile VO2. Using recent quantum Monte Carlo results as the benchmark, all tested semilocal and hybrid functionals as well as the RPA (with PBE inputs) predict the correct magnetic ground states for rutile VO2. The observed paramagnetism could arise from temperature-disordered local spin moments or from the thermal destruction of these moments. All semilocal functionals also give the correct ground-state metallicity for rutile VO2. However, in the ferromagnetic (FM) and antiferromagnetic (AFM) phases, LSDA+U and HSE06 incorrectly predict rutile VO2 to be a Mott-Hubbard insulator. For the computed electronic structures of FM and AFM phases, we find that the Tao-Perdew-Staroverov-Scuseria (TPSS) and revised TPSS (revTPSS) meta-GGAs give strong 2p-3d hybridizations, resulting in a depopulation of the 2p bands of O atoms, in comparison with other tested meta-GGAs. The regularized TPSS (regTPSS) and meta-GGAs made simple, i.e., MGGA_MS0 and MGGA_MS2, which are free of the spurious order-of-limits problem of TPSS and revTPSS, give electronic states close to those of the PBE GGA and LSDA. In comparison to experiment, semilocal functionals predict better equilibrium cell volumes for rutile VO2 in FM and AFM states than in the spin-unpolarized state. For meta-GGAs, a monotonic decrease of the exchange enhancement factor Fx(s,α) with α for small s, as in the MGGA_MS functionals, leads to large (probably too large) local magnetic moments in spin-polarized states.

Volatile organic compounds (VOCs) are pollutants of great interest because they are very harmful for both human health and the environment, even at very low concentrations. In this work we present and discuss the results of the experimental chromatographic study of the role of surface heterogeneity and lateral interactions in the adsorption of volatile organic compounds - ethanol, acetaldehyde and acetone - on the surface of rutile (TiO 2), a typical oxide widely used as a white pigment and a photocatalyst, as well. The ethanol, acetaldehyde and acetone were chosen because they contain the same heteroatom (O) and they have small carbon-chains. The novel method of Reversed Flow-Inverse Gas Chromatography is used, which has a powerful mathematical background and comprises a simple experimental arrangement for the determination of energetic physicochemical quantities directly from the experimental data, by means of a time-resolved analysis. In particular, several important physicochemical quantities are determined, as local adsorption energy, local adsorption isotherm, local monolayer capacity, non-adsorbed gaseous concentration of adsorbate, density probability function for the adsorption energy values, as well as the differential energy of adsorption due to lateral interactions among molecules adsorbed on the heterogeneous solid surface of TiO 2. By means of these quantities, appropriate answers are achieved to critical questions of: (a) What is the type of the adsorption isotherm of a system? (b) Where are the adsorbed molecules located on the heterogeneous surface? (c) What is the nature of the surface bonds? (d) What is the type of non-ideality of the system and (e) How does the adsorbate affect the adsorbent properties?

Metamorphic rutiles occurring in granulite and upper amphibolite facies metapelitic rocks of the Archean Pikwitonei granulite domain (Manitoba) and the Proterozoic Adirondack terrane (New York) give concordant and near concordant UPb ages. The Pb concentrations in rutile range from 2.85 to 168 ppm, U concentrations range from 10.9 to 390 ppm and the measured 206Pb 204Pb ratios range from 182 to 22,100 corresponding to 238U 204Pb ratios of 398-75,100. The proportions of radiogenic 208Pb are very low, ranging from 0.0 to 6.9% of total radiogenic Pb. The habits of the rutile crystals range from stubby to acicular, the physical properties vary from opaque/black to transparent/reddish-brown. Separate batches of black and reddish-brown rutile grains from the same samples have similar U and Pb concentrations, Pb-isotope ratios, and yield the same U Pb ages within analytical uncertainty. No correlation of U concentration and 206Pb 204Pb ratios with morphology or color of the rutiles was observed among the samples analyzed. Most rutiles yield concordant UPb ages which are reproducible within analytical uncertainty, i.e. generally ??2 Ma. The UPb ages for prograde rutile are younger than the time of peak metamorphism given by UPb ages for garnet and zircon, and also younger than UPb ages for sphene and monazite, and 40Ar 39Ar and KAr ages for hornblende but older than 40Ar 39Ar and KAr ages for biotite from the same area. This suggests that the rutile ages reflect cooling below closure temperatures. Within a single hand-specimen, and thus for an identical thermal history, larger rutile grains give older ages than do smaller grains. This suggests that volume diffusion is the most probable mechanism responsible for the ages being younger than the time of peak metamorphism. It also suggests that the dimensions for such diffusion are directly related to the dimensions of the rutile crystal and not to the dimensions of sub-grain domains, as is the case for Ar diffusion in

Atomic adsorption of Au and Pt on the rutile (1 1 0) surface was investigated by atomic-resolution aberration-corrected scanning transmission electron microscopy (STEM) measurements combined with density functional theory calculations. Au single atoms were deposited on the surface in a vacuum condition, and the observed results were compared with Pt single atoms on the same surface prepared by the same experimental manner. It was found that Au single atoms are stably adsorbed only at the bridging oxygen vacancy sites, which is quite different from Pt single atoms exhibiting the most frequently observed adsorption at the basal oxygen vacancy sites. Such a difference in oxygen-vacancy effect between Au and Pt can be explained by electronic structures of the surface vacancies as well as characters of outermost atomic orbitals of Au and Pt.

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

The advent of rutile thermometry brought an increasing interest in understanding rutile formation and its temporal evolution. Here we report progress on several fronts of in situ U-Pb rutile geochronology: (1) Matrix matching, necessary for robust in situ dating is fullfilled by calibrating and testing rutile standards (R10 and R19), including the presentation of new TIMS ages for the rutile standard R19. (2) Common lead correction is routinely applied via 208Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb ages for the other rutile standard and four rutile-bearing metamorphic rocks always agree better than 2% with the reported TIMS ages and other dating studies from the same localities. The methods outlined in this contribution should find wide application in thermochronological studies that require age information of single spots, e.g., single-crystal zoning and texturally-controlled dating. With this information we are able to address the effect of shielding of inclusion phases by robust host minerals.

One-dimensional (1D) TiO2 nanostructures are desirable as photoanodes in dye-sensitized solar cells (DSSCs) due to their superior electron-transport capability. However, making use of the DSSC performance of 1D rutile TiO2 photoanodes remains challenging, mainly due to the small surface area and consequently low dye loading. Herein, a new type of photoanode with a three-dimensional (3D) rutile-nanorod-based network structure directly grown on fluorine-doped tin oxide (FTO) substrates was developed by using a facile two-step hydrothermal process. The resultant photoanode possesses oriented rutile nanorod arrays for fast electron transport as the bottom layer and radially packed rutile head-caps with an improved large surface area for efficient dye adsorption. The diffuse reflectance spectra showed that with the radially packed top layer, the light-harvesting efficiency was increased due to an enhanced light-scattering effect. A combination of electrochemical impedance spectroscopy (EIS), dark current, and open-circuit voltage decay (OCVD) analyses confirmed that the electron-recombiantion rate was reduced on formation of the nanorod-based 3D network for fast electron transport. As a resut, a light-to-electricity conversion efficiency of 6.31% was achieved with this photoanode in DSSCs, which is comparable to the best DSSC efficiencies that have been reported to date for 1D rutile TiO2 .

Nanocrystal samples (particle size about 90 nm) of Eu3+-doped rutile titanium dioxide (TiO2) nanocrystals (rutile Eu3+/TiO2 nanocrystals) were synthesized by the sol-gel method with hydrothermal treatment. The pressure effect on photoluminescence (PL) and Raman spectra of the rutile Eu3+/TiO2 nanocrystals was investigated with a diamond anvil cell under hydrostatic pressure condition. Raman spectra of the samples at high pressures indicated that the critical pressure for the transition from the rutile phase to a new baddeleyite-type phase was between 10 and 14.2 GPa. The position of Raman bands shifted to high wavenumbers and the PL intensity of 5D 0→7F 2 transition of Eu3+ decreased down to zero with the increase of pressure before the phase transition occurred. After releasing the pressure, the rutile phase was not recovered and a α-PbO2-type phase was observed at ambient pressure.

The adsorption of collagen on the reduced rutile (110) surface with monatomic step defects in aqueous solution was modeled by classical molecular dynamics simulation. The step defects on the rutile surface were mainly parallel to the <11bar1> crystal orientation. Possible binding modes including direct and indirect binding modes, that were the peptide interacted with substrate surface directly or via the first layer water molecules, and the structural properties of collagen were discussed in order to analyze the adsorption dynamics of collagen on the reduced rutile surface. The simulation results suggested that the initial poses of collagen on the rutile surface could influence the adsorption conformation of collagen. The reduced rutile surface, which could increase the density of water molecules in the first layer, would provide active sites for collagen adsorption. The direct binding mode was responsible for the stable adsorption of collagen. The indirect binding mode may play an important part at the initial adsorption stage, but itself alone could not ‘trap’ the collagen on the surface stably unless the direct binding mode had already been formed. In addition, the triple helical structure of collagen was sustained by the inner-chain hydrogen bonds among different chains.

The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high -quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.

Negative-ion implantation could be used to create nanoparticles in oxide insulators with finely controlled accuracy for both depth and size. For 50-nm-thick SiO2 film on Si, Ag nanoparticles with 3 nm in diameter were created in the center of the film with distribution thickness of 17 nm. Cu negative-ion implanted silica glass and soda-lime glass showed a high nonlinear susceptance of the 3rd order in nonlinear optical property. Cu and Ag double-implanted silica glass showed an absorption peak between two absorption peaks of surface plasmon resonance (SPR) for Cu and Ag nanoparticles. The optical absorption peak due to SPR of nanoparticle in oxide could be changed by forming nanoparticles with different kinds of elements and alloy. For application of metal nanoparticle to photocatalyst, Ag negative ions were implanted into rutile TiO2. The Ag-implanted rutile samples showed improved photocatalytic efficiency after proper annealing in a decolorization test of methylene blue solution under fluorescent light. The better one was the Ag-implanted rutile TiO2 (Ag: 65 keV, 5×1016 ions/cm2, 500°C annealed), which showed a photocatalytic efficiency higher by 2.2 times than that of unimplanted rutile TiO2. In the evaluation under fluorescent light through UV-cut filter for 19 h, the Ag-implanted rutile showed 6.7 times higher efficiency.

Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile.

Full phonon calculations have been performed to estimate the thermal properties of rutile (titanium dioxide). Calculations have been carried out using the pseudo-potential method within the local density approximation. Thermodynamic properties including the thermal expansion, thermal expansion coefficient, heat capacity and entropy were calculated as a function of temperature in the framework of quasi-harmonic approximation. Also, to compare the results with the results of other approaches, we apply Debye-Slater and Debye-Gruneisen approaches with the same parameters for electronic calculations. It is found that the phonon calculations provide more accurate estimates in comparison with the other two models.

We observed the photo-decomposition process of polystyrene latex (PSL) spheres on a rutile TiO₂(110) single crystal surface by using atomic force microscopy. During the decomposition process, both the height and width of the PSL spheres linearly decreased with the irradiation time in a similar way from the beginning, suggesting that the PSL spheres are isotropically decomposed. This indicates that the interface between the PSL spheres and the TiO₂ surface is not a dominant reaction site, as expected from normal photocatalytic reactions.

The authors report "field-programmable rectification" in crystals of rutile TiO2. A "programming" voltage is applied between two Pt electrodes on the surface of a crystal. Afterwards, current can pass in the direction of the programming voltage, but not in the reverse direction. The polarity of the rectification can be reversed by applying a programming voltage of opposite sign. The effect was observed on the (110) and (100) surfaces, but not the (001) surface. The proposed mechanism is field-induced motion of oxygen vacancies, which pile up under the negative terminal, eliminating a Schottky barrier, but leaving one at the positive terminal intact.

Surfactants are widely used as templates to control the nucleation and growth of nanostructured metal oxides such as titania. To gain insight into the origin of surfactant-titania interactions responsible for polymorph and orientation selection, we simulate the self-assembly of an anionic surfactant monolayer on various low-index titania surfaces and for a range of densities. We characterize the binding in each case and compute the adhesion energies, finding anatase (100) and rutile (110) to be the strongest-binding surfaces. The sodium counterions in the monolayer are found to dominate the adhesion. It is also observed that the assembly is directed predominantly by surface-monolayer electrostatic complementarity.

TiO{sub 2} films with various Sn concentrations were deposited on quartz substrates using rf reactive magnetron sputtering. The crystal structure was investigated by using x-ray diffraction, Raman spectroscopy, and transmission electron microscopy, and the chemical states of Ti and Sn were analyzed by x-ray absorption near edge structure (XANES) spectroscopy. Without Sn doping, TiO{sub 2} films change the crystal structure from rutile to anatase as the total gas pressure increases in the sputtering deposition. On the other hand, Sn doping induces the transformation of TiO{sub 2} crystalline structure from anatase to rutile phase, where the XANES spectra implied that Sn substitutes into Ti site of rutile TiO{sub 2}. Atomic force microscope analyses revealed that the Sn-doped TiO{sub 2} films exhibited a flat surface with the roughness of approximately 2 nm.

The reported values of bandgap of rutile GeO{sub 2} calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (∼2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO{sub 2} using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Γ-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Γ-M direction changes towards a linear dispersion with volume expansion.

A shock-induced polymorph (TiO2II) of anatase and rutile has been identified in breccias from the late Eocene Chesapeake Bay impact structure. The breccia samples are from a recent, partially cored test hole in the central uplift at Cape Charles, Virginia. The drill cores from 744 to 823 m depth consist of suevitic crystalline-clast breccia and brecciated cataclastic gneiss in which the TiO2 phases anatase and rutile are common accessory minerals. Electron-microprobe imaging and laser Raman spectroscopy of TiO2 crystals, and powder X-ray diffraction (XRD) of mineral concentrates, confirm that a high-pressure, ??-PbO2 structured polymorph of TiO2 (TiO2II) coexists with anatase and rutile in matrix-hosted crystals and in inclusions within chlorite. Raman spectra of this polymorph include strong bands at wavenumbers (cm-1) 175, 281, 315, 342, 356, 425, 531, 571, and 604; they appear with anatase bands at 397, 515, and 634 cm-1, and rutile bands at 441 and 608 cm-1. XRD patterns reveal 12 lines from the polymorph that do not significantly interfere with those of anatase or rutile, and are consistent with the TiO2II that was first reported to occur naturally as a shock-induced phase in rutile from the Ries crater in Germany. The recognition here of a second natural shock-induced occurrence of TiO2II suggests that its presence in rocks that have not been subjected to ultrahigh-pressure regional metamorphism can be a diagnostic indicator for confirmation of suspected impact structures.

A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO(2) nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport and a factor four lower defect state density than conventional rutile nanoparticle films.

The effect of the rutile content on the photovoltaic performance of dye-sensitized solar cells (DSSCs) composed of mixed-phase TiO(2) photoelectrode has been investigated. The mixed-phase TiO(2) particles with varied amounts of rutile, relative to anatase phase, are synthesized by an in situ method where the concentration of sulfate ion is used as a phase-controlling parameter in the formation of TiO(2) using TiCl(4) hydrolysis. The surface area (S(BET)) varies from 33 (pure rutile) to 165 (pure anatase) m(2) g(-1). Generally, both the current density (J(sc)) and photo-conversion efficiency (η) decrease as the rutile content increases. The incorporation of rod-shaped rutile particles causes low uptake of dye due to the reduced surface area, as well as slow electron transport in less efficiently-stacked structure. However, maximum J(sc) (14.63 mA cm(-2)) and η (8.69%) appear when relatively low rutile content (16%) is employed. The reported synergistic effect by the efficient interparticle electron transport from rutile to anatase seems to overbalance the decrease of surface area when small amount of rutile particles is incorporated.

A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO2 nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport (see picture) and a factor four lower defect state density than conventional rutile nanoparticle films.

The thin films for pure TiO2 and that incorporated with Cu ion were deposited by DC magnetron co-sputtering with Ar gas. The crystal texture, surface morphology, energy gap and optical properties of the prepared films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectrometer (XPS), UV-vis spectrophotometer, and Raman spectroscopy. The results show that as-deposited TiO2 film mainly possesses anatase structure at room temperature with pure Ar gas, but the introduction of Cu can alter the phase structure of crystallite TiO2. XRD patterns and Raman spectra indicate that the Cu incorporation with high concentration (ACu/ATi + ACu ≈ 20%) favors the formation of rutile phase. Moreover, the Cu incorporation into TiO2 lattice induces band gap narrowing. Band structures and density of states have been analyzed based on density functional theory (DFT) and periodic models in order to investigate the influence of the Cu incorporation on the electronic structure of TiO2. Both experimental data and electronic structure calculations evidence the fact that the change in film structure from the anatase to the rutile phase can be ascribed to the possible incorporation of Cu1+ in the sites previously occupied by Ti4+, and the presence of Cu results in important effect on the electronic states, which is mainly related to the 3d Cu orbitals in the gap and in the vicinity of the valence band edges for TiO2.

Nanostructuring of surfaces and two-dimensional materials using swift heavy ions offers some unique possibilities owing to the deposition of a large amount of energy localized within a nanoscale volume surrounding the ion trajectory. To fully exploit this feature, the morphology of nanostructures formed after ion impact has to be known in detail. In the present work the response of a rutile TiO2 (001) surface to grazing-incidence swift heavy ion irradiation is investigated. Surface ion tracks with the well known intermittent inner structure were successfully produced using 23 MeV I ions. Samples irradiated with different ion fluences were investigated using atomic force microscopy and grazing-incidence small-angle X-ray scattering. With these two complementary approaches, a detailed description of the swift heavy ion impact sites, i.e. the ion tracks on the surface, can be obtained even for the case of multiple ion track overlap. In addition to the structural investigation of surface ion tracks, the change in stoichiometry of the rutile TiO2 (001) surface during swift heavy ion irradiation was monitored using in situ time-of-flight elastic recoil detection analysis, and a preferential loss of oxygen was found.

The electrochemical properties of the rutile-type TiO2 and Nb-doped TiO2 were investigated for the first time as Na-ion battery anodes. Ti(1-x)Nb(x)O2 thick-film electrodes without a binder and a conductive additive were prepared using a sol-gel method followed by a gas-deposition method. The TiO2 electrode showed reversible reactions of Na insertion/extraction accompanied by expansion/contraction of the TiO2 lattice. Among the Ti(1-x)Nb(x)O2 electrodes with x = 0-0.18, the Ti(0.94)Nb(0.06)O2 electrode exhibited the best cycling performance, with a reversible capacity of 160 mA h g(-1) at the 50th cycle. As the Li-ion battery anode, this electrode also attained an excellent rate capability, with a capacity of 120 mA h g(-1) even at the high current density of 16.75 A g(-1) (50C). The improvements in the performances are attributed to a 3 orders of magnitude higher electronic conductivity of Ti(0.94)Nb(0.06)O2 compared to that of TiO2. This offers the possibility of Nb-doped rutile TiO2 as a Na-ion battery anode as well as a Li-ion battery anode.

The coverage-dependent adsorption behavior of acetic acid (CH3COOH) on rutile TiO2(110) was investigated by means of density functional theory (DFT) calculations, corrected by on-site Coulomb corrections and long-range dispersion interactions. The p(2 × 1) and c(2 × 2) domains of dissociatively adsorbed acetic acid under different coverages have been studied in detail regarding their structural and energetic properties. Adsorptions of formic acid (HCOOH) and carbonic acid (H2CO3) were also considered for better understanding the adsorption behaviors of carboxylic acids. Our calculation results show that carboxylic acids prefer to dissociatively adsorb in bridging bidentate configuration, and it induces significant surface relaxation at the adsorption site, which also affects other surface atoms nearby. Interestingly, we have shown that such adsorption-induced relaxations still maintain bond symmetries for surface Ti cations within the p(2 × 1) domain while they are drastically broken within the c(2 × 2) domain, giving rise to unstable Ti cations at the surface. This work not only explains the long-lasting puzzle of the preferable occurrence of p(2 × 1) domain for the adsorbed carboxylic acids at rutile TiO2(110), it also proposes a novel scheme that metal oxide surfaces may follow when they are involved in the processes like surface functionalization and self-assembly.

Rutile filled PTFE composites have been fabricated through Sigma Mixing, Extrusion, Calendering and Hot pressing (SMECH) process. Dielectric constant (\\varepsilonr') and loss tangent (tan δ) of filled composites at microwave frequency region were measured by waveguide cavity perturbation technique using a Vector Network Analyzer. The temperature coefficient of dielectric constant (tau_{\\varepsilonr'}) was measured in the 0-100°C temperature range. In order to tailor the temperature coefficient of dielectric constant of the composite, thermoplastic Poly (ether ether ketone) (PEEK) has been used as a secondary polymer. Flexible laminate having a dielectric constant, \\varepsilonr'˜10.4, loss tangent tan δ˜0.0045 and tau_{\\varepsilonr'}˜-40 ppm/K was realized in Polytetrafluroethylene (PTFE)/rutile composites with the addition of 8 wt% PEEK. The reduction in tau_{\\varepsilonr'} is mainly attributed to the positive tau_{\\varepsilonr'} of PEEK and increased interface region in the composites as a result of the PEEK addition.

Take into account the fact that the natural rutile utilized for the production of titanium dioxide pigment through chloride process is desperately lacking worldwide especially in China, an attempt was exploited for extracting synthetic rutile from Yunnan ilmenite concentrate with hydrochloric acid pressure leaching process. The leaching parameters for one step leaching process were investigated. The results shown that the optimum condition is leaching temperature of 413 K (140 °C), acid concentration of 20 pct HCl, leaching time of 4 hours and liquid/solid mass ratio of 8:1. A two steps leaching process was also suggested to reutilize the leaching liquor which with a high content of HCl. The results showed that the content of HCl decreased from 135 to 75 g/L, total iron increased from 44.5 g/L to about 87.6 g/L, and the liquid/solid mass ratio decreased to 5:1 with a two steps leaching process. The leaching product produced through a two steps leaching process shows a pure golden red with a high content of titanium (92.65 pct TiO2), a relatively low content of calcium (0.10 pct CaO) and magnesium (0.12 pct MgO), but high content of silicon (5.72 pct SiO2).

Nanostructuring of surfaces and two-dimensional materials using swift heavy ions offers some unique possibilities owing to the deposition of a large amount of energy localized within a nanoscale volume surrounding the ion trajectory. To fully exploit this feature, the morphology of nanostructures formed after ion impact has to be known in detail. In the present work the response of a rutile TiO2 (001) surface to grazing-incidence swift heavy ion irradiation is investigated. Surface ion tracks with the well known intermittent inner structure were successfully produced using 23 MeV I ions. Samples irradiated with different ion fluences were investigated using atomic force microscopy and grazing-incidence small-angle X-ray scattering. With these two complementary approaches, a detailed description of the swift heavy ion impact sites, i.e. the ion tracks on the surface, can be obtained even for the case of multiple ion track overlap. In addition to the structural investigation of surface ion tracks, the change in stoichiometry of the rutile TiO2 (001) surface during swift heavy ion irradiation was monitored using in situ time-of-flight elastic recoil detection analysis, and a preferential loss of oxygen was found. PMID:27738417

Take into account the fact that the natural rutile utilized for the production of titanium dioxide pigment through chloride process is desperately lacking worldwide especially in China, an attempt was exploited for extracting synthetic rutile from Yunnan ilmenite concentrate with hydrochloric acid pressure leaching process. The leaching parameters for one step leaching process were investigated. The results shown that the optimum condition is leaching temperature of 413 K (140 °C), acid concentration of 20 pct HCl, leaching time of 4 hours and liquid/solid mass ratio of 8:1. A two steps leaching process was also suggested to reutilize the leaching liquor which with a high content of HCl. The results showed that the content of HCl decreased from 135 to 75 g/L, total iron increased from 44.5 g/L to about 87.6 g/L, and the liquid/solid mass ratio decreased to 5:1 with a two steps leaching process. The leaching product produced through a two steps leaching process shows a pure golden red with a high content of titanium (92.65 pct TiO2), a relatively low content of calcium (0.10 pct CaO) and magnesium (0.12 pct MgO), but high content of silicon (5.72 pct SiO2).

Rutile (TiO₂) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 °C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300–500 °C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at ~1 GPa and 700–800 °C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 μg/g as temperature increases from 300 to 500 °C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 μg/g at 300 to 500 °C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. The Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 μg/g as temperature increases from 300 to 500 °C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 °C at ≥2 GPa, but there is no observed

Rutile (TiO2) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 °C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300-500 °C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at similar to 1 GPa and 700-800 °C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 mu g/g as temperature increases from 300 to 500 °C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 mu g/g at 300 to 500 °C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. Here, the Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 mu g/g as temperature increases from 300 to 500 °C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 °C at ≥ 2 GPa, but

Rutile (TiO2) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 °C). Inmore » this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300-500 °C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at similar to 1 GPa and 700-800 °C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 mu g/g as temperature increases from 300 to 500 °C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 mu g/g at 300 to 500 °C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. Here, the Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 mu g/g as temperature increases from 300 to 500 °C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 °C at ≥ 2 GPa, but there

We investigated the oxidation of Ir(111) by gas-phase oxygen atoms at temperatures between 500 and 625 K using temperature programmed desorption (TPD), low energy electron diffraction (LEED), low energy ion scattering spectroscopy (LEISS) and density functional theory (DFT) calculations. We find that a well-ordered surface oxide with (√ 3 × √ 3)R30° periodicity relative to Ir(111) develops prior to the formation of a rutile IrO2(100) layer. The IrO2(100) layer reaches a saturation thickness of about four oxide layers under the oxidation conditions employed, and decomposes during TPD to produce a single, sharp O2 desorption peak at 770 K. Favorable lattice matching at the oxide-metal interface is likely responsible for the preferential growth of the IrO2(100) facet during the initial oxidation of Ir(111), with the resulting coincidence lattice generating a clear (6 × 1) moiré pattern in LEED. Temperature programmed reaction spectroscopy (TPRS) experiments reveal that CO and H2O molecules bind only weakly on the IrO2(100) surface and LEISS measurements show that the oxide surface is highly enriched in O-atoms. These characteristics provide strong evidence that the rutile IrO2(100) layer is oxygen-terminated, and thus lacks reactive Ir atoms that can strongly bind molecular adsorbates. Oxygen binding energies predicted by DFT suggest that on-top O-atoms will remain adsorbed on IrO2(100) at temperatures up to 625 K, thus supporting the conclusion that the rutile IrO2 layer grown in our experiments is oxygen-terminated. As such, the appearance of only a single O2 TPD peak indicates that the singly coordinate, on-top O-atoms remain stable on the IrO2(100) surface up to temperatures at which the oxide layer begins to thermally decompose.

In the present study, the biosynthesis of rutile TiO2 nanoparticles (TiO2 NPs) was achieved by a novel, biodegradable and convenient procedure using fruit peel Annona squamosa aqueous extract. This is the first report on the new, simple, rapid, eco-friendly and cheaper methods for the synthesis of rutile TiO2 NPs at lower temperature using agricultural waste. Rutile TiO2 NPs were characterized by UV, XRD, SEM, TEM and EDS studies. The UV-Vis spectrophotometer results were promising and showed a rapid production of TiO2 NPs with a surface plasmon resonance occurring at 284 nm. The formation of the TiO2 NPs as observed from the XRD spectrum is confirmed to be TiO2 particles in the rutile form as evidenced by the peaks at 2θ = 27.42°, 36.10°, 41.30° and 54.33° when compared with the literature. The TEM images showed polydisperse nanoparticles with spherical shapes and size 23 ± 2 nm ranges.

In the present study, the biosynthesis of rutile TiO(2) nanoparticles (TiO(2) NPs) was achieved by a novel, biodegradable and convenient procedure using fruit peel Annona squamosa aqueous extract. This is the first report on the new, simple, rapid, eco-friendly and cheaper methods for the synthesis of rutile TiO(2) NPs at lower temperature using agricultural waste. Rutile TiO(2) NPs were characterized by UV, XRD, SEM, TEM and EDS studies. The UV-Vis spectrophotometer results were promising and showed a rapid production of TiO(2) NPs with a surface plasmon resonance occurring at 284 nm. The formation of the TiO(2) NPs as observed from the XRD spectrum is confirmed to be TiO(2) particles in the rutile form as evidenced by the peaks at 2θ=27.42°, 36.10°, 41.30° and 54.33° when compared with the literature. The TEM images showed polydisperse nanoparticles with spherical shapes and size 23±2 nm ranges.

The availability of low-index rutile TiO2 single crystal substrates with atomically flat surfaces is essential for enabling epitaxialgrowth of rutile transition metal oxide films. The high surface energy of the rutile (001) surface often leads to surface faceting, which precludes the sputter and annealing treatment commonly used for the preparation of clean and atomically flat TiO2(110) substrate surfaces. In this work, we reveal that stable and atomically flat rutile TiO2(001) surfaces can be prepared with an atomically ordered reconstructedsurface already during a furnace annealing treatment in air. We tentatively ascribe this result to the decrease in surface energy associated with the surface reconstruction, which removes the driving force for faceting. Despite the narrow temperature window where this morphology can initially be formed, we demonstrate that it persists in homoepitaxialgrowth of TiO2(001) thin films. The stabilization of surface reconstructions that prevent faceting of high-surface-energy crystal faces may offer a promising avenue towards the realization of a wider range of high quality epitaxial transition metal oxide heterostructures.

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(II) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO{sub 2} (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO{sub 2}. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

Nanotechnology is extensively used in industry and is widely explored for possible applications in medicine. However, its potential respiratory and systemic adverse effects remain unknown. Here pure titanium dioxide (TiO2) nanorods with rutile structure were prepared at room temperature by using a soft chemistry technique. The structure of the TiO2 rutile nanorods was confirmed by powder X-ray diffraction, and the size was revealed by transmission electron microscopy. Thereafter, we investigated, in Wistar rats, the acute (24-hr) effects of intratracheal instillation of these rutile TiO2 nanorods (1 and 5 mg/kg) on lung inflammation (assessed by bronchoalveolar lavage), systemic inflammation, and platelet aggregation in whole blood. Compared with vehicle-exposed rats, rats that underwent intratracheal instillation of TiO2 nanorods experienced a dose-dependent increase in macrophage numbers at 1 (+50%) and 5 mg/kg (+81%; P < 0.05) and an influx of neutrophils at 1 (+294%) and 5 mg/kg (+4117%; P < 0.01) in their bronchoalveolar lavage fluid. Both doses of rutile TiO2 nanorods caused pulmonary and cardiac edema, assessed by analysis of the wet weight-to-dry weight ratios. Similarly, the numbers of monocytes and granulocytes in the blood were increased in a dose-dependent manner after exposure to rutile TiO2 nanorods. In contrast, the number of platelets was significantly reduced after pulmonary exposure to 5 mg/kg TiO2 nanorods; this result indicated the occurrence of platelet aggregation in vivo. The direct addition of TiO2 nanorods (0.4-10 microg/ml) to untreated rat blood significantly induced platelet aggregation in a dose-dependent fashion in vitro. It is concluded that the intratracheal instillation of rutile TiO2 nanorods caused upregulation of lung inflammation, pulmonary and cardiac edema, and systemic inflammation. Rutile TiO2 nanorods also triggered platelet aggregation in vivo and in vitro.

Both the anatase (A) and rutile (R) phases of titanium oxide have shown enhanced antimicrobial and bioactivity levels but the specific A/R phase ratio needed for the best results is still unknown. In this study titanium samples were anodized to produce specific ratios of anatase and rutile phases within the oxide layers. Specific ratios produced included maximum A minimum R, minimum A maximum R, 50% A 50% R, minimum A minimum R, and a non-anodized titanium control group. Samples were characterized for phase distributions within the oxide layers, surface porosity, corrosion resistance, and bioactivity. Results indicated the targeted phase ratios were reproducibly achieved during the anodization process. Samples containing the highest levels of anatase showed the largest individual pore sizes, but a lower overall percent porosity value compared to samples containing higher rutile levels. EBSD examination of the anodized layer cross-sections provided valuable new spatial information on the distribution of anatase and rutile phases within the anodized layers. Highly porous oxide layers showed significantly higher corrosion rates compared to non-anodized titanium, but no significant differences were shown in the icorr values between samples containing primarily anatase phase, samples containing primarily rutile phase, and samples containing an approximate 50:50 mixture of the two phases. Minimum A minimum R samples showed substantially less porosity compared to the other anodization groups, a significantly lower oxide thickness, and comparable corrosion rates to non-anodized titanium. All samples within the study showed apatite production in simulated body fluid within the seven day test period indicating enhanced bioactivity.

Present study investigates the photoabsorption properties of single crystal rutile TiO2 (110) surfaces after they have been implanted with low fluences of cobalt ions. The surfaces, after implantation, demonstrate fabrication of nanostructures and anisotropic nano-ripple patterns. Creation of oxygen vacancies (Ti3+ states), development of cobalt nano-clusters as well as band gap modifications have also been observed. Results presented here demonstrate that fabrication of self organized nanostructures, upon implantation, along with the development of oxygen vacancies and ligand field transitions of cobalt ion promote the enhancement of photo-absorbance in both UV (∼2 times) and visible (∼5 times) regimes. These investigations on nanostructured TiO2 surfaces can be important for photo-catalysis.

The confluence of electron correlations and spin-orbit interactions is critical to realizing quantum phases in 5 d transition metal oxides. Here, we investigate how the strength of the effective electron correlations evolve across a series of d5 iridates comprised of IrO6 octahedra, ranging from the layered correlated insulator Sr2IrO4 , to the three-dimensional perovskite semimetal SrIrO3, to metallic rutile IrO2 in which the octahedra are arranged in a mixed edge and corner sharing network. Through a combination of reactive oxide molecular-beam epitaxy, in situ angle-resolved photoemission spectroscopy, core level photoemission, and density functional theory, we show how the effective electron correlations weaken as a function of increasing connectivity of the IrO6 network and p -d hybridization. Our results demonstrate how structure and connectivity can be used to control the strength of correlations in the iridates.

Electronic transport properties of the single-crystalline titanium dioxide (TiO2) nanorods (NRs) with single rutile phase have been investigated. The conductivity values for the individual TiO2 NRs grown by metal-organic chemical vapor deposition are in the range of 1-10 Ω-1 cm-1. The temperature-dependent measurement shows the presence of two shallow donor levels/bands with activation energies at 8 and 28 meV, respectively. On the photoconductivity (PC), the TiO2 NRs exhibit the much higher normalized PC gain and sensitive excitation-power dependence than the polycrystalline nanotubes. The results demonstrate the superior photoconduction efficiency and distinct mechanism in the monocrystalline one-dimensional TiO2 nanostructures in comparison to the polycrystalline or nanoporous counterparts.

The results of photoconductivity studies of hydrogen donors in ZnO and rutile TiO2 are presented. It is shown that local vibrational modes of O-H bonds comprising donors in both semiconductors can be detected in photoconductivity spectra as Fano resonances at 3611 and 3290 cm-1 in the case of ZnO and TiO2, respectively. The frequencies of these features red-shift in energy down to 2668 (ZnO) and 2445 cm-1 (TiO2) if hydrogen is substituted by deuterium. Based on the frequency of the deuterium resonance it is concluded that the ionization energy of the hydrogen donor in TiO2 is less than 300 meV, which is in variance with predictions of theory. The reasons for such a discrepancy are discussed.

We have explored the correlation between the Seebeck coefficient and the electronic structure of nanostructured rutile MnO2 using density functional theory to critically appraise the three orders of magnitude scatter in literature data. Our hypothesis is that the microstructure and morphology on the nanoscale is causing this behaviour, which we have tested by comparing the Seebeck coefficient of bulk MnO2 with two low-energy surfaces: MnO2(1 1 0) and MnO2(0 0 1). From these data, it is evident that variations over two orders of magnitude in the Seebeck coefficient can be attained by affecting domain size and texture on the nanoscale. This may be understood by analysing the electronic structure. Surface hybridized Mn d-O p states fill the band gap of MnO2 and thus substantially alter the transport properties.

We report on the structural, electrical, and optical properties of 5% niobium doped TiO2 thin films grown on various substrates by pulsed laser deposition. The epitaxial anatase Nb:TiO2 film on LaAlO3 is shown to be an intrinsic transparent metal and its metallic property arises from Nb substitution into Ti site as evidenced by the Rutherford backscattering channeling result. In contrast, the rutile Nb:TiO2 thin films show insulating behaviors with 2-3 orders higher room temperature electrical resistivity and ˜30 times lower mobility. A blueshift in the optical absorption edge is observed in both phases, though of differing magnitude.

The surface chemistry of oxygen and oxygenates on Rutile TiO2(110) is of great interest for various applications such as heterogeneous catalysis and photo catalysis. Though it is generally accepted that surface defects are active sites, the role of subsurface defects is under debate. We have therefore investigated the influence of the bulk defect density on the reductive coupling of benzaldehyde to stilbene as a model system. Using IRRAS we identify stilbene diolate as a reduction intermediate. The concentration of this intermediate is proportional to the bulk defect density, whereas adsorption of benzaldehyde at lower temperatures is not affected, which indicates a dominant role of Ti interstitials at temperatures above 400 K.

The diffusion of CO{sub 2} molecules on a reduced rutile TiO{sub 2}(110)-(1×1) surface has been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM feature associated with a CO{sub 2} molecule at an oxygen vacancy (V{sub O}) becomes increasingly streaky with increasing temperature, indicating thermally activated CO{sub 2} diffusion from the V{sub O} site. From temperature-dependent tunneling current measurements, the barrier for diffusion of CO{sub 2} from the V{sub O} site is estimated to be 3.31 ± 0.23 kcal/mol. The corresponding value from the DFT calculations is 3.80 kcal/mol. In addition, the DFT calculations give a barrier for diffusion of CO{sub 2} along Ti rows of only 1.33 kcal/mol.

In this paper, in order to improve the photocatalytic application of TiO2, the low-density material such as Ps and TiCl4 is proposed to be the raw carrier, and the nana-structured TiO2 composite is obtained by combining the sol-gel technology and layer-by-layer self-assembly methods; The pure rutile nano-structured TiO2 whose diameter is about 0.25mm are prepared under different conditions at low temperature. By being calcined under 450 ℃ the hollow sphere TiO2 is prepared and its composition, size, structure analysis and characterization are studied by using X ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetric analysis (DSC-TG) respectively.

Shielded metal arc wet welding, due to its flexibility and ease of mobilization, is one of the most attractive methods for repair of underwater structures. However, the quality of the weld metals deposited by this process is detrimentally affected by the direct contact of the welding arc with the aqueous environment. Oxygen and hydrogen generated by the decomposition of water in the arc are responsible for the main problems related to this specific process: loss of deoxidizers, oxygen pickup, increase in oxide inclusions content, hydrogen-induced cracking, and porosity. Rutile electrodes are recognized in the literature as being able to deposit welds with adequate mechanical properties but with high hydrogen content. Oxidizing electrodes, on the other hand, are able to deposit welds with lower hydrogen content but higher oxygen content. Welds deposited by rutile electrodes presented approximately 90 ml/100g of diffusible hydrogen while oxidizing electrodes produced welds with diffusible hydrogen contents varying from 40 to 50 ml/100g. It was found that the measured diffusible hydrogen contents of underwater wet welds are more dependent on the type of electrode covering than on the weld metal oxygen content. The residual hydrogen content of underwater welds showed a tendency to increase to a constant level of approximately 5 ml/100g as the oxygen content of the weld increased to the saturation value (0.22 wt.pct.). It seems, therefore, that the diffusible hydrogen content of underwater wet welds is more influenced by the amount of total hydrogen absorbed by the liquid metal before solidification than by the amount of inclusions, acting as hydrogen traps, in the weld metal.

Titanium dioxide (TiO2) is well-known as an active photocatalyst for degradation of various organic pollutants. Over the years, a wide range of TiO2 nanoparticles with different phase compositions, crystallinities, and surface areas have been developed. Due to the different methods and conditions used to synthesize these commercial TiO2 nanoparticles, the properties and photocatalytic performance would also be different from each other. In this study, the photocatalytic removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5- trichlorophenoxyacetic acid (2,4,5-T) was investigated on commercial Evonik P25, Evonik P90, Hombikat UV100 and Hombikat N100 TiO2 nanoparticles. Upon photocatalytic tests, it was found that overall, the photocatalytic activities of the P25 and the P90 were higher than the N100 and the UV100 for the removal of both 2,4-D and 2,4,5-T. The high activities of the P25 and the P90 could be attributed to their phase compositions, which are made up of a mixture of anatase and rutile phases of TiO2. Whereas, the UV100 and the N100 are made up of 100% anatase phase of TiO2. The synergistic effect of the anatase/rutile mixture was reported to slow down the recombination rate of photogenerated electron-hole pairs. Consequently, the photocatalytic activity was increased on these TiO2 nanoparticles.

The pressure-induced phase transition of rutile-structured TiO2 was investigated by in-situ Raman spectrum method in a laser-heated diamond anvil cell (DAC). The experiment was conducted at 35 GPa under quasihydrostatic conditions using argon as medium. At room temperature, the rutile-type TiO2 begins to transform to baddeleyite-type phase at 13.4 GPa and completes at 21 GPa, and this new high-pressure structure retains up to 35 GPa, the upmost pressure used in this study. At the pressure of 29.4 GPa the sample of baddeleyite-type TiO2 was heated by an YAG laser to about 1 000-1500 degrees C, and then the baddeleyite phase transformed to a Pbca phase. The Pbca phase was heated again at 35.0 GPa and it was still stable. The sample then began to be decompressed, and the Pbca phase of TiO2 transformed to baddeleyite structure at 26.3 GPa, which stayed stable to 11.4 GPa. The formation of Pbca phase from baddeleyite phase needs the condition of high temperature, it transforms back to badde-leyite structure completely at pressure of a little below that on its formation, which suggests the boundary of the two phases can be determined at about 28 GPa. At 7. 6 GPa, and the Raman spectrum shows the characteristics of the mixture of two phases of baddeleyite-type and alpha-PbO2-type, which indicates that the baddeleyite phase transforms to alpha-PbO2 phase at about 7 GPa. The alpha-PbO2-type TiO2 is metastable under ambient condition.

Here we report results of systematic investigation of heterogeneity and disorder in Ti{sub 1-x}Fe{sub y}O{sub 2-d} nanorod rutile-based flowerlike aggregates. It was found that Ti{sub 1-x}Fe{sub y}O{sub 2-d} aggregates are composed of two crystalline phases: rutile as a dominant and anatase as a minor phase. Flowerlike aggregates were found to grow from an isometric core ca. 5-10 nm in diameter that was built from anatase and rutile nanorods ca. 5 x 100 nm that were grown on the anatase surface having base plane (001) intergrowth with an anatase plane. The direction of rutile nanorods growth, i.e., direction of the nanorod elongation, was [001]. Highly nonisometric rutile crystals produce anisotropic X-ray powder diffraction line broadening and doubling of vibrational bands in Raman spectra. Both these techniques confirmed nonisometric character of rutile crystals and gave a quantitative measure of crystal shape anisotropy in excellent agreement with high-resolution transmission electron microscopy measurements. In addition, from the atomic pair distribution function and Raman spectral analyses the level of vacancy concentration was determined in rutile and anatase phases of investigated samples.

A new process of catalytic autoclave desiliconization of the leucoxene concentrate by lime milk with the formation of synthetic rutile and wollastonite is developed. The general laws of the processes occurring under the conditions of pressure leaching of the concentrate are revealed, and the main leaching parameters that ensure selective desiliconization of leucoxene grains are determined. The leucoxene concentrate is shown to contain rare and rare-earth elements. They are concentrated in synthetic rutile during desiliconization, which facilitates their extraction during subsequent chlorination of rutile.

The geometry, energy and stretching frequency of carbon monoxide on the rutile TiO2(110) surface for coverages between 0.125 and 1.5 ML are investigated by means of density functional theory calculations. Four different approaches were considered, namely, the PBE exchange-correlation functional and the PBE-D2, vdW-DF and vdW-DF2 methods incorporating van der Waals dispersion interactions of different theoretical complexity and empiricism. It is found that upon the increase of the surface coverage, the adsorption becomes less favorable due to lateral destabilizing interactions between adsorbed molecules. The preferred geometry for CO changes from an upright configuration at 0.125 ML to tilted configurations at 1.5 ML and the tilting of the C-O axis from the surface normal increases with the increase of the surface coverage. At 1 ML, all computational approaches predict alternate tilted configurations which contradict the interpretation of recent experimental infrared reflection-absorption spectroscopic findings suggesting upright CO geometries. Encouragingly, a very good agreement between calculated and experimental shifts of the C-O stretching frequency of adsorbed CO at different coverages with respect to gaseous CO species was reached.

Mixed-metal oxide monolayer grown at an oxide support is of great potential in applications like heterogeneous catalysis. In this work, the experimentally obtained ordered mixed FeTiO3 oxide monolayer supported by rutile TiO2(011) surface has been carefully studied with density functional theory calculations. The genetic algorithm based optimization scheme has been employed to improve the searching capacity for possible structures, and a well ordered mixed Fe(II)Ti(IV)O3 monolayer oxide structure much more stable than the one proposed previously has been successfully located. The new surface structure consists of uniformly distributed Ti and Fe cations in the ratio of 2:1. The simulated Scanning Tunneling Microscopy image based on this model is well consistent with the experimental one. Our calculations have shown that the O vacancy formation energy is rather high at the surface. We have also studied the adsorption of O2 and CO at the exposed Fe sites on the surface as well as their reactions. The adsorption energies of O2 are generally higher than those of CO. The catalytic cycle of CO oxidation following an Eley-Rideal type mechanism has been located for CO to react with surface adsorbed O2 and O.

Inelastic light scattering intensities in response to magnetic excitations are governed by magnetooptic coupling coefficients, which have been previously evaluated, for instance, for the ferrimagnetic Y3Fe5O12 (YIG) and the metamagnetic FeCl2 and FeBr2. However, by far the most detailed studies to date were performed on the classic rutile-structure antiferromagnets, and here we summarize the results obtained from the many experimental and theoretical investigations of these compounds for both one-magnon and two-magnon excitations. A comparison of the magnitudes of the various coupling coefficients for MnF2, FeF2, CoF2, and NiF2 reveals a surprising similarity in many coefficients. In one-magnon Raman scattering the in-phase linear magnetooptic coefficient dominates, and the main differences between MnF2, FeF2, and NiF2 lie in the relative significance of the in-phase quadratic magnetooptic coefficient. Thus, the quadratic coefficients now appear to be of particular importance in determining the strength of one-magnon scattering in a variety of magnetic insulators. In two-magnon Raman scattering one magnetooptic coefficient is dominant for all of these antiferromagnets. However, the other six coefficients are in general remarkably similar in magnitude and not negligible in most cases, indicating some similarity in the way light interacts with the pairs of magnons of opposite and equal wave vectors in rutile structure antiferromagnets.

Rutile TiO2 microflowers with three-dimensional spiky flower like architecture at the nanometer level are obtained by a fast single step surfactant free ethylene glycol based solvothermal scheme of synthesis. These structures are characterized by X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and Raman spectroscopy. These measurements confirm Rutile phase of TiO2 flowers with very high crystallinity. Photodegradation of Rhodamine B with UV exposure is investigated by UV-Visible spectroscopy measurements in the presence of these samples. They are shown to have high photocatalytic activity due to the large surface area contributed by the highly dense spiky nanostructures. The plasmonic (Au) loading in these structures are shown to significantly enhance the photocatalytic activity.

We report the rutile titania-based capture of ATP and its application as a MALDI-MS target plate. This chip, when immersed in solutions containing different concentrations of ATP, can capture ATP and lead to its successful detection in MALDI-MS. We have optimized the ideal surface, showing an increased capture efficacy of the 900 °C (rutile) titania surfaces. We demonstrate the use of this chip as a target plate for direct analysis of the attached ATP using MALDI-MS, down to attomolar concentrations. This chip has a promising future for the detection of ATP in environmental samples, which may eventually be used as a pollution indicator in particular environments.

A systematic study on the photocatalytic activity of well-defined, macroscopic bulk single-crystal TiO{sub 2} anatase and rutile samples has been carried out, which allows us to link photoreactions at surfaces of well-defined oxide semiconductors to an important bulk property with regard to photochemistry, the life time of e-h pairs generated in the bulk of the oxides by photon absorption. The anatase (101) surface shows a substantially higher activity, by an order of magnitude, for CO photo-oxidation to CO{sub 2} than the rutile (110) surface. This surprisingly large difference in activity tracks the bulk e-h pair lifetime difference for the two TiO{sub 2} modifications as determined by contactless transient photoconductance measurements on the corresponding bulk materials.

A compositional feature that distinguishes subduction-related lavas from oceanic basalts is depletion of the high field strength elements (HFSE), such as Ti, Zr, Nb, and Ta [1,2]. Similar depletions also characterize many continental basalts [3,4], and have been inferred for the bulk continental crust [5,6]. Because the HFSE are compatible in rutile (TiO2), it has been posited that their depletion in island arc basalts (IAB) is due to its presence as a residual phase, either in the subducted oceanic crust or the mantle wedge. Here I present results from new experiments that investigate the influences of pressure, temperature, and composition on the partitioning of Zr4+, Nb5+, Hf4+, and Ta5+ between rutile and silicate melt. These results demonstrate that low-degree partial melting of rutile-bearing subducted oceanic crust would produce significant, identifiable fractionations among the HFSE, providing a test for the nature of the subduction component. Experiments were carried out on 2 SiO2-Al2O3-MgO-CaO-Na2O-K2O base melt compositions (rhyodacite; basalt). Rutile saturation was achieved by adding 10-40 wt% TiO2. Each starting composition was doped with ZrO2, Nb2O5, HfO2, and Ta2O5. Low-pressure experiments were carried out using sealed Pt capsules in a vertical quenching furnace. High pressure experiments were carried out in graphite capsules using a solid-medium piston-cylinder device. The major element composition of glass and rutile, as well as the trace element content of the rutile, were determined by electron microprobe. The trace element content of the glass was determined SIMS. At 1 bar and temperatures of 1250 ° to 1450 °C the concentration of TiO2 at rutile saturation is significantly higher in the basalt (17-38 wt%) than the rhyodacite (5-12 wt%). Rutile-melt partition coefficients for the HFSE are higher for the rhyodacite than for the basalt by a factor of ~2-5. Partition coefficients for Nb5+ and Ta5+ are larger than those for Zr4+ and Hf4+ in all

TiO(2) nanoparticles were prepared by one-step pulsed laser ablation of a titanium target immersed in a poly-(vinylpyrrolidone) solution at room temperature. The products were systematically characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). The results indicated that the rutile TiO(2) nanocrystalline particles were one-step synthesized at room temperature and the mean size in diameter is about 50 nm with a narrow size distribution. A probable formation process was proposed on the basis of the microstructure and the instantaneous plasma plume induced by the laser. Photocatalytic activity was monitored by degradation of a methylene blue solution. The as-prepared rutile TiO(2) nanoparticles demonstrate a good photocatalytic performance. This work shows that pulsed laser ablation in liquid media is a good method to synthesize some nanosized materials which are difficult to produce by other conventional methods.

Highly crystalline rutile with a specific surface area as high as 280 m(2) g(-1) and well-connected uniform mesoporosity has been synthesized by rigid templating using commercial, low-cost polyether block amide. This general, simple synthesis route for high surface-area mesoporous nanocrystalline oxides and nanocomposite membranes is important for catalysis, sensors, energy storage, solar cells, heavy metal removal and separations.

The TiO2 films are prepared by atomic layer deposition (ALD) method using titanium isopropoxide precursors at 250 °C and analyzed using resonant photoemission spectroscopy (resPES). We report on the Ti2p and O1s core levels, on the valence band (VB) spectra and x-ray absorption spectroscopy (XAS) data, and on the resonant photoelectron spectroscopy (resPES) profiles at the O1s and the Ti3p absorption edges. We determine the elemental abundance, the position of the VB maxima, the partial density of states (PDOS) in the VB and in the conduction band (CB) and collect these data in a band scheme. In addition, we analyze the band-gap states as well as the intrinsic states due to polarons and charge-transfer excitations. These states are found to cause multiple Auger decay processes upon resonant excitation. We identify several of these processes and determine their relative contribution to the Auger signal quantitatively. As our resPES data allow a quantitative analysis of these defect states, we determine the relative abundance of the PDOS in the VB and in CB and also the charge neutrality level. The anatase and rutile polymorphs of TiO2 are analyzed in the same way as the TiO2 ALD layer. The electronic properties of the TiO2 ALD layer are compared with the anatase and rutile polymorphs of TiO2. In our comparative study, we find that ALD has its own characteristic electronic structure that is distinct from that of anatase and rutile. However, many details of the electronic structure are comparable and we benefit from our spectroscopic data and our careful analysis to find these differences. These can be attributed to a stronger hybridization of the O2p and Ti3d4s states for the ALD films when compared to the anatase and rutile polymorphs.

The temperature dependence of the Nuclear Quadrupole Interaction on 44Sc in rutile was measured by Time Differential Perturbed Angular Correlation in the temperature range from 300 K to 945 K. Whereas \\upomega _Q = eQV_zz/4hbar with Vzz denoting the largest component of the electric field gradient tensor in magnitude increases with increasing temperature, the asymmetry parameter η remains essentially constant. This observation fits into the systematic with other probes provided the sign of Vzz is negative.

Of the three crystallographic allotropes of nanocrystalline titania (rutile, anatase and brookite), anatase exhibits the greatest potential for a variety of applications, especially in the area of catalysis and sensors. However, with rutile being thermodynamically the most stable phase, anatase tends to transform into rutile on heating to temperatures in the range of 500 degrees C to 700 degrees C. Efforts made to stabilize the anatase phase at higher temperatures by doping with metal oxides suffer from the problems of having a large amorphous content on synthesis as well as the formation of secondary impurity phases on doping. Recent studies have suggested that the as-synthesised phase composition, crystallite size, initial surface area and processing conditions greatly influence the anatase to rutile transformation temperature. In this study nanocrystalline titania was synthesised in the anatase form bya chemical vapour synthesis (CVS) method using titanium tetra iso-propoxide (TTIP) as a precursor under varying flow rates of oxygen and helium. The anatase to rutile transformation was studied using high temperature X-ray diffraction (HTXRD) and simultaneous thermogravimetric analysis (STA), followed by transmission electron microscopy (TEM). It was demonstrated that the anatase-rutile transformation temperatures were dependent on the oxygen to helium flow rate ratio during CVS and the results are presented and discussed.

In this work the preparation, deposition and structural properties of titanium oxide (TiO2) thin films were investigated. The films were deposited by means of the e-beam physical vapor deposition (EBPVD) method in high vacuum (10-7 Torr). A controlled deposition rate in the range of 0.1-0.3 Å/s was monitored in situ employing quartz crystal. The films were deposited on the oxidized Si (1 0 0) wafer, glass micro slides. These films were analyzed using Grazing Angle X-ray diffraction (GA-XRD), Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy (RAMAN), Atomic Force Microscopy (AFM) and UV-visible Spectroscopy (UV-vis). Structural characterization results showed mainly presence of the crystalline rutile phase, however an interfacial SiO2 layer between TiO2 and the substrate and the minor anatase crystalline phase of TiO2 was also identified in FTIR analysis. Grain size was found to be in the range of 100-125 nm while grain boundary was estimated to be 20 nm. Direct and indirect optical band gap was estimated to be 3.64 and 3.04 eV, respectively. A process induced self annealing of deposited film shows a strong effect on the structural, morphological and optical properties. Furthermore, low deposition rate and high vacuum allows rutile to rutile phase transformation from indigenously prepared TiO2 target to thin film.

A facile green method to synthesize uniform nanostructured urchinlike rutile TiO2 is demonstrated. Titanium trichloride was selected as the TiO2 precursor, and a mixed solvent containing H2O and ethylene glycol was used. By using this binary medium, the nucleation and crystal growth of rutile TiO2 can be regulated, giving rise to very uniform urchinlike structures with tailorable sizes. As confirmed by the SEM and TEM analysis, large particles with dense aggregation of needle-like building blocks or small ones with loosely packed subunits could be obtained at different reaction conditions. The as-prepared samples were applied as the anode material for lithium-ion batteries, and they were shown to have superior properties with a high reversible capacity of 140 mA h g(-1) at a high current rate of 10 C for up to 300 cycles, which is almost unmatched by other rutile TiO2-based electrodes. A stable capacity of 88 mA h g(-1) can also be delivered at an extremely high rate of 50 C, suggesting the great potential of the as-prepared product for high-rate lithium-ion batteries.

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

The polycyclic aromatic hydrocarbons (PAHs) in crumb tyre rubber were firstly degraded under UV irradiation in the presence of rutile TiO2 and hydrogen peroxide. The effects of light intensity, catalyst amount, oxidant amount, initial pH value, co-solvent content, and reaction time on degradation efficiency of typical PAHs in crumb tyre rubber were studied. The results indicated that UV irradiation, rutile TiO2, and hydrogen peroxide were beneficial to the degradation of PAHs and co-solvent could accelerate the desorption of PAHs from crumb tyre rubber. Up to 90% degradation efficiency of total 16 PAHs could be obtained in the presence of rutile TiO2 (1 wt%) and hydrogen peroxide (1.0 mL) under 1800 µW cm(-2) UV irradiation for 48 h. The high molecular weight PAHs (such as benz(a)pyrene) were more difficult to be degraded than low molecular weight PAHs (such as phenanthrene, chrysene). Moreover, through the characterization of reaction solution and degradation products via GC-MS, it was proved that the PAHs in crumb tyre rubber were successfully degraded.

We report for the first time, using a simple and environmentally benign chemical method, the low temperature synthesis of densely populated upright-standing rutile TiO2 nanoplate films onto a glass substrate from a mixture of titanium trichloride, hydrogen peroxide and thiourea in triply distilled water. The rutile TiO2 nanoplate films (the phase is confirmed from x-ray diffraction analysis, selected area electron diffraction, energy-dispersive x-ray analysis, and Raman shift) are 20-35 nm wide and 100-120 nm long. The chemical reaction kinetics for the growth of these upright-standing TiO2 nanoplate films is also interpreted. Films of TiO2 nanoplates are optically transparent in the visible region with a sharp absorption edge close to 350 nm, confirming an indirect band gap energy of 3.12 eV. The Brunauer-Emmet-Teller surface area, Barret-Joyner-Halenda pore volume and pore diameter, obtained from N2 physisorption studies, are 82 m2 g - 1, 0.0964 cm3 g - 1 and 3.5 nm, respectively, confirming the mesoporosity of scratched rutile TiO2 nanoplate powder that would be ideal for the direct fabrication of nanoscaled devices including upcoming dye-sensitized solar cells and gas sensors.

Anatase and rutile biphasic nanostructured titania (TiO(2)) has been synthesized via hydrolysis of titanium tetraisopropoxide in an aqueous solution of hydrobromic acid (HBr) and N,N-dimethylformamide (DMF) at 80 degrees C for 16 h. The presence of DMF, which was partially hydrolyzed during the process, determined the formation of a biphasic material. Powder x-ray diffraction showed the presence of both anatase and rutile titania phases in a ratio of approx. 1:1. Transmission electron microscope analysis showed that rutile was present as radial flower-like nanorods, which were surrounded by anatase spherical nanoparticles of 5 nm diameter. Low temperature nitrogen adsorption-desorption analysis showed the characteristic hysteresis loop of a mesoporous material. Specific surface area reached a value of 120 m(2) g(-1) and the average pore diameter was 50 A. X-ray photoelectron spectroscopic analysis revealed that interstitial nitrogen was incorporated (0.35 at.%) during the annealing process. According to ultraviolet (UV)-visible diffuse reflectance spectroscope characterization, the N-doping caused a bandgap reduction from 3.0 to 2.9 eV. Photocatalytic activity of the material was tested for the degradation of methylene blue, methyl orange and 4-nitrophenol under near-UV and visible light radiation.

Anatase and rutile biphasic nanostructured titania (TiO2) has been synthesized via hydrolysis of titanium tetraisopropoxide in an aqueous solution of hydrobromic acid (HBr) and N,N-dimethylformamide (DMF) at 80 °C for 16 h. The presence of DMF, which was partially hydrolyzed during the process, determined the formation of a biphasic material. Powder x-ray diffraction showed the presence of both anatase and rutile titania phases in a ratio of approx. 1:1. Transmission electron microscope analysis showed that rutile was present as radial flower-like nanorods, which were surrounded by anatase spherical nanoparticles of 5 nm diameter. Low temperature nitrogen adsorption-desorption analysis showed the characteristic hysteresis loop of a mesoporous material. Specific surface area reached a value of 120 m2 g-1 and the average pore diameter was 50 Å. X-ray photoelectron spectroscopic analysis revealed that interstitial nitrogen was incorporated (0.35 at.%) during the annealing process. According to ultraviolet (UV)-visible diffuse reflectance spectroscope characterization, the N-doping caused a bandgap reduction from 3.0 to 2.9 eV. Photocatalytic activity of the material was tested for the degradation of methylene blue, methyl orange and 4-nitrophenol under near-UV and visible light radiation.

A new bioinspired hierarchical nanofibrous silver-nanoparticle/anatase-rutile-titania (Ag-NP/A-R-titania) composite was fabricated by employing a natural cellulose substance (e.g., commercial laboratory cellulose filter paper) as the structural scaffold template, which was composed of anatase-phase titania (A-titania) nanotubes with rutile-phase titania (R-titania) nanoneedles grown on the surfaces and further silver nanoparticles (AgNPs) immobilized thereon. As it was employed as an anode material for lithium-ion batteries (LIBs), high reversible capacity, enhanced rate performance, and excellent cycling stability were achieved as compared with those of the corresponding cellulose-substance-derived nanotubular A-titania, R-titania, heterogeneous anatase/rutile titania (A-R-titania) composite, and commercial P25 powder. This benefited from its unique porous cross-linked three-dimensional structure inherited from the initial cellulose substance scaffold, which enhances the sufficient electrode/electrolyte contact, relieves the severe volume change upon cycling, and improves the amount of lithium-ion storage; moreover, the high loading content of the silver component in the composite improves the electrical conductivity of the electrode. The structural integrity of the composite was maintained upon long-term charge/discharge cycling, indicating its significant stability.

Pure rutile phase titanium oxides (TiO2) nanocrystals were synthesized via hydrothermal method with titanium tetrachloride (TiCl4) and water (H2O) treated in an autoclave. The particle size and phase assemblages were characterized using Scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. Band gap energy (Eg) of the nanocrystals was estimated from the Ultra violet - visible light (UV-vis) absorption spectra. It was demonstrated that TiO2 nanocrystals can be prepared through increasing of temperature and period of treatment. It is believed that the presence of acid chloride (HCl) as by-product during the hydrolysis played an important role in controlling the growth of morphology and crystal structures. The Eg of the samples were estimated from the plot of modified Kubelka-Munk function were in the range of 3.04 - 3.26eV for the samples synthesized at temperature ranging from 50 to 200°C for 16 hours.

This work presents thermochemical data for possible gas phase intermediate species in an industrial rutile chlorinator. An algorithm developed for previous work is employed to ensure that all possible species are considered, reducing the number of important species neglected. Thermochemical data and enthalpies of formation are calculated for 22 new species using density functional theory, post Hartree-Fock coupled cluster calculations, and statistical mechanics. Equilibrium calculations are performed to identify whether any Ti/C intermediates are likely to be important to the high temperature industrial process. These new species are not present at high concentration in the exit stream. It is therefore likely that the two chemical processes do not interact. Rather, the Cl₂ rapidly reacts with the solid TiO₂ to form TiCl₄ and O₂. The latter then reacts with the solid C to form CO and CO₂ and provide the heat. Data for all the new species is provided as Supporting Information. Finally, a new methodology for data collaboration is investigated in which the data is made openly accessible using the resource description framework. Example scripts are provided to demonstrate how to query and retrieve the data automatically.

Dense and well-oriented rutile TiO2 nanorod arrays were synthesized on a titanium substrate using the organic compound dibutyltin dilaurate as the oxygen source in the oxidation of Ti at 850 °C. The influence of temperature on the nanostructured TiO2 formation and the effect of the TiO2 structures on their wettability were also investigated. Polycrystalline TiO2 grains were formed at 800 °C; in contrast, TiO2 micro-whiskers were grown on the Ti substrate at 900 °C. The measurement of the water contact angle shows that the wetting property of the TiO2 films strongly depends on their surface structure. The surface of the dense well-oriented nanorod arrays is highly hydrophobic with a water contact angle of 130 °C. This study has demonstrated that the direct oxidation of Ti substrate using an organic oxygen source is a promising method for fabrication of large scale, uniform and well-aligned TiO2 nanorod arrays on titanium substrates.

Photogenerated charge carrier dynamics near molecule/TiO2 interfaces are important for the photocatalytic and photovoltaic processes. To understand this fundamental aspect, we performed a time-domain ab initio nonadiabatic molecular dynamics study of the photogenerated hole dynamics at the CH3OH/rutile TiO2(110) interface. We studied the forward and reverse hole transfer between TiO2 and CH3OH as well as the hole energy relaxation to the valence band maximum. First, we show that the hole-trapping ability of CH3OH depends strongly on the adsorption structure. Only when the CH3OH is deprotonated to form chemisorbed CH3O will ∼15% of the hole be trapped by the molecule. Second, we find that strong fluctuations of the HOMO energies of the adsorbed molecules induced by electron-phonon coupling provide additional channels, which accelerate the hole energy relaxation. Third, we demonstrate that the charge transfer and energy relaxation processes depend significantly on temperature. When the temperature decreases from 100 to 30 K, the forward hole transfer and energy relaxation processes are strongly suppressed because of the reduction of phonon occupation. These results indicate that the molecule/TiO2 energy level alignment, thermal excitation of a phonon, and electron-phonon coupling are the key factors that determine the photogenerated hole dynamics. Our studies provide valuable insights into the photogenerated charge and energy transfer dynamics at molecule/semiconductor interfaces.

A novel biosensor platform comprising of the functionalized sputtered rutile nanostructured titanium dioxide (nTiO2) for rapid detection of estrogenic substance (bisphenol A) has been proposed. The direct current (DC) sputtering of titanium (Ti) on glass substrate has been converted to ordered nanostructured TiO2 film via oxidation. The nanostructured TiO2 surface was functionalized with self-assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) and glutaraldehyde. The enzyme molecule, tyrosinase (Tyrs) has been covalently immobilized on the surface of APTES modified nanostructured TiO2 film. To investigate the crystalline structure and surface morphology of functionalized nTiO2/Ti electrode, the X-ray diffraction, scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy have been carried out. This impedimetric biosensor exhibits a comparable sensitivity (361.9 kΩ/µM) in a wide range of detection (0.01-1.0 µM) and a response time of 250 s for bisphenol A (BPA) monitoring. This novel manufacturing process for nTiO2 film is cheap, practical and safer for functionalization with SAM and glutaraldehyde to improve the biosensor efficacy. The strong protein absorption capability of the nTiO2 surface demonstrates an excellent electrochemical biosensor and could be useful for the detection of other phenolic compounds.

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

Pure rutile phase titanium oxides (TiO{sub 2}) nanocrystals were synthesized via hydrothermal method with titanium tetrachloride (TiCl{sub 4}) and water (H{sub 2}O) treated in an autoclave. The particle size and phase assemblages were characterized using Scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. Band gap energy (E{sub g}) of the nanocrystals was estimated from the Ultra violet – visible light (UV-vis) absorption spectra. It was demonstrated that TiO{sub 2} nanocrystals can be prepared through increasing of temperature and period of treatment. It is believed that the presence of acid chloride (HCl) as by-product during the hydrolysis played an important role in controlling the growth of morphology and crystal structures. The E{sub g} of the samples were estimated from the plot of modified Kubelka-Munk function were in the range of 3.04 – 3.26eV for the samples synthesized at temperature ranging from 50 to 200°C for 16 hours.

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption ofmore » n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

The shielded metal arc welding (SMAW) and flux cored arc welding (FCAW) processes use covered electrodes and flux cored wire as consumables. Among these consumables, ones containing rutile are the most widely used, and since they have a considerable natural radioactive content, they can be considered as NORM (naturally occurring radioactive material). To calculate the effective dose on workers during their use in a conservative situation, samples of slag and aerosols and particles emitted or deposited during welding were taken and measured by gamma, alpha and beta spectrometry. An analytical method was also developed for estimating the activity concentration of radionuclides in the inhaled air. (222)Rn activity concentration was also assessed. With all these data, internal and external doses were calculated. The results show that external doses are negligible in comparison with internal ones, which do not exceed 1 mSv yr(-1), either in this conservative situation or in any other more favourable one. Radionuclides after Rn in the radioactive natural series are emitted at the same activity concentration to the atmosphere, this being around 17 times higher than that corresponding to radionuclides before Rn. Taking into account these conclusions and the analytical method developed, it can be concluded that one way to assess the activity concentration of natural radionuclides in inhaled air and hence effective doses could be the early gamma-ray spectrometry of aerosols and particles sampled during the welding process.

Uniform nanoparticles of rutile and anatase were prepared, respectively, by a new approach, a microemulsion-mediated method, in which the microemulsion medium was further treated by hydrothermal reaction. Herein, the combined procedure of microemulsion and hydrothermal synthesis to prepare nanoparticles is referred to as a microemulsion-mediated hydrothermal (MMH) method. This MMH method could lead to the formation of crystalline titania powders under much milder reaction conditions than the normally reported microemulsion-mediated methods, in which posttreatment of calcination was necessary. In this work, a kind of solution was formed by dissolving tetrabutyl titanate into hydrochloric acid or nitric acid, and the solution was dispersed in an organic phase for the preparation of the microemulsion medium. The aqueous cores of water/Triton X-100/hexanol/cyclohexane microemulsions were used as constrained microreactors for a controlled growth of titania particles under hydrothermal conditions. The product of hydrothermal synthesis was separated and dried for characterization. The phase components and the morphologies and grain sizes of products were determined by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). The effects of changing the variables of the reaction conditions, such as the use of acid, the concentrations of acid, the reaction temperatures, and/or the reaction times on the phases and morphologies of the titania product are described.

The interactions of ethylene glycol (EG) with partially reduced rutile TiO2(110) surface have been studied using temperature programmed desorption (TPD). The saturation coverage on the surface Ti rows is determined to be 0.43 monolayer (ML), slightly less than one EG per two Ti sites. Most of the adsorbed ethanol (~80%) undergoes further reactions to other products. Two major channels are observed, dehydration yielding ethylene and water and dehydrogenation yielding acetaldehyde and hydrogen. Hydrogen formation is rather surprising as it has not been observed previously on TiO2(110) from simple organic molecules. The coverage dependent yields of ethylene and acetaldehyde correlate well with that of water and hydrogen, respectively. Dehydration dominates at lower EG coverages (< 0.2 ML) and plateaus as the coverage is increased to saturation. Dehydrogenation is observed primarily at higher EG coverages (>0.2 ML). Our results suggest that the observed dehydration and dehydrogenation reactions proceed via different surface intermediates.

Adsorbate-induced band gap states in semiconductors are of particular interest due to the potential of increased light absorption and photoreactivity. A combined theoretical and experimental (STM, photoemission) study of the molecular-scale factors involved in the formation of gap states in TiO(2) is presented. Using the organic catechol on rutile TiO(2)(110) as a model system, it is found that the bonding geometry strongly affects the molecular electronic structure. At saturation catechol forms an ordered 4 x 1 overlayer. This structure is attributed to catechol adsorbed on rows of surface Ti atoms with the molecular plane tilted from the surface normal in an alternating fashion. In the computed lowest-energy structure, one of the two terminal OH groups at each catechol dissociates and the O binds to a surface Ti atom in a monodentate configuration, whereas the other OH group forms an H-bond to the next catechol neighbor. Through proton exchange with the surface, this structure can easily transform into one where both OH groups dissociate and the catechol is bound to two surface Ti in a bidentate configuration. Only bidendate catechol introduces states in the band gap of TiO(2).

The electronic properties of RO 2 (R=Si, Ge, Sn and Pb; a group IVA element) compounds in rutile structure have been calculated using WIEN2k implementation of full potential linearized augmented plane wave (FPLAPW) method. The exchange and correlation (XC) effects are taken into account by an orbital independent modified Becke Johnson (MBJ) potential as coupled with Local Density Approximation (LDA) for all the compounds except for PbO 2 where only Generalized Gradient Approximation (GGA) is considered for the same. We predict a direct band gap in all these compounds with continuous decrease as the atomic size of IVA element increases such that there is an appearance of semimetallic band structure for the last compound, PbO 2. The largest band gap (7.66 eV) has been found for SiO 2, which governs its insulating nature. We observe that MBJLDA results for band gaps of these compounds are far better than those obtained using GGA and Engel-Vosko's GGA (EV-GGA). A very good agreement is observed between MBJLDA band gaps with corresponding experimental values as compared to other calculations. The electronic band structures are also analyzed in terms of contributions from various electrons.

Remarkable room-temperature ferromagnetism was observed both in undoped and Cu-doped rutile TiO2 single crystals (SCs). To tune their magnetism, Ar ion irradiation was quantitatively performed on the two crystals in which the saturation magnetizations for the samples were enhanced distinctively. The post-irradiation led to a spongelike layer in the near surface of the Cu-doped TiO2. Meanwhile, a new CuO-like species present in the sample was found to be dissolved after the post-irradiation. Analyzing the magnetization data unambiguously reveals that the experimentally observed ferromagnetism is related to the intrinsic defects rather than the exotic Cu ions, while these ions are directly involved in boosting the absorption in the visible region. Project supported by the National Natural Science Foundation of China (Grant No. 11575074), the Open Project of State Key laboratory of Crystal Material, Shandong University, China (Grant No. KF1311), the Open Project of Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, China (Grant No. LZUMMM2012003), the Open Project of Key Laboratory of Beam Technology and Material Modification of Ministry of Education, Beijing Normal University, China (Grant No. 201204), and the Fundamental Research Funds for the Central Universities, China (Grant No. lzujbky-2015-240).

In view of the increasing usage of anatase and rutile crystalline phases of titania NPs in the consumer products, their entry into the aquatic environment may pose a serious risk to the ecosystem. In the present study, the possible toxic impact of anatase and rutile nanoparticles (individually and in binary mixture) was investigated using freshwater microalgae, Chlorella sp. at low exposure concentrations (0.25, 0.5 and 1mg/L) in freshwater medium under UV irradiation. Reduction of cell viability as well as a reduction in chlorophyll content were observed due to the presence of NPs. An antagonistic effect was noted at certain concentrations of binary mixture such as (0.25, 0.25), (0.25, 0.5), and (0.5, 0.5) mg/L, and an additive effect for the other combinations, (0.25, 1), (0.5, 0.25), (0.5, 1), (1, 0.25), (1, 0.5), and (1, 1) mg/L. The hydrodynamic size analyses in the test medium revealed that rutile NPs were more stable in lake water than the anatase and binary mixtures [at 6h, the sizes of anatase (1mg/L), rutile NPs (1mg/L), and binary mixture (1, 1mg/L) were 948.83±35.01nm, 555.74±19.93nm, and 1620.24±237.87nm, respectively]. The generation of oxidative stress was found to be strongly dependent on the crystallinity of the nanoparticles. The transmission electron microscopic images revealed damages in the nucleus and cell membrane of algal cells due to the interaction of anatase NPs, whereas rutile NPs were found to cause chloroplast and internal organelle damages. Mis-shaped chloroplasts, lack of nucleus, and starch-pyrenoid complex were noted in binary-treated cells. The findings from the current study may facilitate the environmental risk assessment of titania NPs in an aquatic ecosystem.

The effect of calcination temperature and time on structural and textural changes of two commercial TiO{sub 2} samples (pure anatase and a mixture of anatase and rutile) has been investigated using N{sub 2} physisorption, ex-situ and in-situ X-ray powder diffraction, differential scanning calorimetry and UV–vis diffuse reflectance spectroscopy. The increase of the calcination temperature (up to 700 °C) and time (up to 8 h) causes only textural changes in the pure anatase, whereas a transformation of the anatase to rutile takes place, in addition, in the mixed titania (containing anatase and rutile). The textural changes observed in pure anatase sample were attributed to solid state diffusion leading to an increase in the size of anatase nanocrystals, through sintering. Thus, the mean pore diameter shifts to higher values and the pore volume and specific surface area decrease. The successful application of the Johnson–Mehl–Avrami–Kolmogorov model in the kinetic data concerning the pure anatase indicates a mass transfer control of sintering process. Similar textural changes were also observed upon calcination of the sample containing anatase and rutile. In this case not only sintering but the anatase to rutile transformation contributes also to the textural changes. Kinetic analysis showed that the rutile nanocrystals in the mixed titania served as seed for by-passing the high energy barrier nucleation step allowing/facilitating thus the anatase to rutile transformation. A fine control of the anatase to rutile ratio and thus of energy-gap and the population of hetero-junctions may be obtained by adjusting the calcination temperature and time. - Graphical Abstract: Dependence of anatase content of P25 on the calcination temperature (600 °C (■), 650 °C (●), 700 °C (▲)) and time. - Highlights: • Increase of calcination temperature up to 800 °C and time up to 8 h causes only textural changes in pure anatase • Progressive transformation of anatase

Photochemistry of the molecularly and dissociatively adsorbed forms of methanol on the vacuum-annealed rutile TiO2(110) surface was explored using temperature programmed desorption (TPD), both with and without coadsorbed water. Methoxy, and not methanol, was confirmed as the photochemically active form of adsorbed methanol on this surface. UV irradiation of methoxy-covered TiO2(110) lead to depletion of the methoxy coverage and formation of formaldehyde and a surface OH group. Coadsorbed water did not promote either molecular methanol photochemistry or thermal decomposition of methanol to methoxy. However, terminal OH groups (OHt), prepared by coadsorption of water and oxygen atoms, thermally converted molecularly adsorbed methanol to methoxy at 120 K, thus enabling photoactivity. While chemisorbed water molecules had no influence on methoxy photochemistry, water molecules hydrogen-bonded in the second layer to bridging oxygen (Obr) sites inhibited the methoxy photodecomposition to formaldehyde. From this we conclude that Obr sites accept protons from the hole-mediated conversion of methoxy to formaldehyde. These results provide new fundamental understanding of the hole-scavenging role of methanol in photochemical processes on TiO2-based materials and how water influences this photochemistry. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle under contract DEAC05-76RL01830. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

The interactions of CO2 with oxygen adatoms (Oa’s) on rutile TiO2(110) surfaces have been studied using scanning tunneling microscopy. At 50 K CO2 is found to adsorb preferentially on five-coordinated Ti sites (Ti5c’s) next to Oa’s rather than on oxygen vacancies (VO’s) (the most stable adsorption sites on reduced TiO2(110)). Temperature dependent studies show that after annealing to 100 - 150 K, VO’s become preferentially populated indicating the presence of a kinetic barrier for CO2 adsorption into the VO’s. The difference between the CO2 binding energy on VO’s and Ti5c sites next to the Oa’s are found to be only 0.009 - 0.025 eV. The barrier for CO2 diffusion away from Oa’s is estimated to be ~0.17 eV. Crescent-like feature of the images of CO2 adsorbed on Ti5c’s next to Oa’s are interpreted as a time average of terminally bound CO2 molecules switching between the configurations that are tilted towards Oa and/or towards one of the two neighboring bridging oxygen (Ob) rows. In the presence of VO defects, CO2 is found to tilt preferentially away from the VO containing Ob row. If another CO2 is present on the neighboring Ti5c row, both CO2 molecules tilt towards the common Ob row that separates them.

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C1–C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar to previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2–C4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.

Rutile U-Pb thermochronology is applied successfully by both TIMS and beam methods to date cooling events in mafic and metapelitic rocks, as well as in detrital studies. The Zr-in-rutile thermometer is very robust to thermal diffusion, and generally requires complete recrystallization to change recorded crystallization temperatures. Evidence for diffusion of HFSE elements in rutile is sparse; whereas U-Pb chronology generally records diffusion controlled cooling from the last event. This study follows conventional thermobarometry and U-Pb TIMS results on monazite, sphene and rutile of Möller et al. (1995) establishing a 2 Ga eclogite facies event from MORB-like metabasic, and metapelitic rocks in the Usagaran Orogen of Tanzania, interpreted to be the oldest outcrops of subduction-related eclogites. Rutile from both rock types were discordant near a ca. 500 Ma lower intercept, confirming a thermal overprint postulated on the basis of K-Ar and Rb-Sr mica ages by e.g. Wendt et al. (1972). The age of the eclogite-facies event was confirmed by U-Pb zircon dating of a 1991±2 Ma crosscutting pegmatite (Collins et al., 1999). We present in situ LA-ICP-MS rutile petrochronology on five metabasic and metapelitic eclogite facies samples with variable retrograde amphibolite-facies recrystallization. Thermometry confirms conventional Fe-Mg results, including higher peak temperatures in metabasites. Traverses on rutile inclusions in large garnet prophyroblasts in metapelites show increasing temperatures from cores outwards and a slight decrease towards outermost rims, with peak T coinciding with highest Mg# and highest grossular content, hence consistent with preservation of prograde zoning in the garnets and a brief eclogite facies event. Large rutiles (800μm) in recrystallized samples record temperature zoning profiles. U-Pb results show inheritance of near concordant 2 Ga domains, but dominantly confirm the ca. 490 Ma amphibolite facies overprint. The study is an excellent

The rutile TiO{sub 2} (110) (1x1) surface is considered the prototypical ''well-defined'' system in the surface science of metal oxides. Its popularity results partly from two experimental advantages: bulk-reduced single crystals do not exhibit charging, and stoichiometric surfaces--as judged by electron spectroscopes--can be prepared reproducibly by sputtering and annealing in oxygen. We present results that show that this commonly-applied preparation procedure may result in a surface structure that is by far more complex than generally anticipated. Flat, (1x1) terminated surfaces are obtained by sputtering and annealing in ultrahigh vacuum. When re-annealed in oxygen at moderate temperatures (470 K to 660 K), irregular networks of partially-connected, pseudohexagonal rosettes (6.5 x 6 {angstrom} wide), one-unit cell wide strands, and small ({approximately} tens of {angstrom}) (1x1) islands appear. This new surface phase is formed through reaction of oxygen gas with interstitial Ti from the reduced bulk. Because it consists of an incomplete, kinetically-limited (1x1) layer, this phenomenon has been termed restructuring. We report a combined experimental and theoretical study that systematically explores this restructuring process. The influence of several parameters (annealing time, temperature, pressure, sample history, gas) on the surface morphology is investigated using STM. The surface coverage of the added phase as well as the kinetics of the restructuring process are quantified by LEIS and SSIMS measurements in combination with annealing in {sup 18}O-enriched gas. Atomic models of the essential structural elements are presented and are shown to be stable with first-principles density functional calculations. The effect of oxygen-induced restructuring on surface chemistry and its importance for TiO{sub 2} and other bulk-reduced oxide materials is briefly discussed.

Recombination of photo-generated charges is one of the most significant challenges in designing efficient photo-anode for photo electrochemical water oxidation. In the case of TiO2, mixed phase (anatase-rutile) junctions often shown to be more effective in suppressing electron-hole recombination compared to a single (anatase or rutile) phase. Here, we report the study of bulk and surface recombination process in TiO2 multi-leg nanotube (MLNTs) anatase-rutile (A-R) junctions decorated with reduced graphene oxide (rGO) layers, through an analysis of the photo-current and impedance characteristics. To quantify the charge transport/transfer process involved in these junctions, holes arriving at the interface of semiconductor/electrolyte were collected by adding H2O2 to the electrolyte. This enabled us to interpret the bulk and surface recombination process involved in anatase/rutile/rGO junctions for photo-electrochemical water oxidation. We correlated this quantification to the electrochemical impedance spectroscopy (EIS) measurements, and showed that in anatase/rutile junction the increase in PEC performance was due to suppression in electron-hole recombination rate at the surface states that effectively enhances the hole transfer rate to the electrolyte. On the other hand, in rGO wrapped A-R MLNTs junction it was due to both phenomenon i.e decrease in bulk recombination rate as well as increase in hole transfer rate to the electrolyte at the semiconductor/electrolyte interface.

The reaction mechanisms for selective acetylene hydrogenation on three different supports, Pd4 cluster, oxygen defective anatase (101), and rutile (110) titania supported Pd4, cluster are studied using the density functional theory calculations with a Hubbard U correction (DFT+U). The present calculations show that the defect anatase support binds Pd4 cluster more strongly than that of rutile titania due to the existence of Ti3+ in anatase titania. Consequently, the binding energies of adsorbed species such as acetylene and ethylene on Pd4 cluster become weaker on anatase supported catalysts compared to the rutile supported Pd4 cluster. Anatase catalyst has higher selectivity of acetylene hydrogenation than rutile catalyst. On the one hand, the activation energies of ethylene formation are similar on the two catalysts, while they vary a lot on ethyl formation. The rutile supported Pd catalyst with lower activation energy is preferable for further hydrogenation. On the other hand, the relatively weak adsorption energy of ethylene is gained on anatase surface, which means it is easier for ethylene desorption, hence getting higher selectivity. For further understanding, the energy decomposition method and micro-kinetic analysis are also introduced.

Dye-sensitized solar cells (DSSCs) based on hierarchical rutile TiO(2) flower clusters prepared by a facile, one-pot hydrothermal process exhibit a high efficiency. Complex yet appealing rutile TiO(2) flower films are, for the first time, directly hydrothermally grown on a transparent conducting fluorine-doped tin oxide (FTO) substrate. The thickness and density of as-grown flower clusters can be readily tuned by tailoring growth parameters, such as growth time, the addition of cations of different valence and size, initial concentrations of precursor and cation, growth temperature, and acidity. Notably, the small lattice mismatch between the FTO substrate and rutile TiO(2) renders the epitaxial growth of a compact rutile TiO(2) layer on the FTO glass. Intriguingly, these TiO(2) flower clusters can then be exploited as photoanodes to produce DSSCs, yielding a power conversion efficiency of 2.94% despite their rutile nature, which is further increased to 4.07% upon the TiCl(4) treatment.

The contiguous region between Guangxi, Guizhou, and Yunnan, commonly referred to as the Golden Triangle region in SW China, hosts many Carlin-type gold deposits. Previously, the ages of the gold mineralization in this region have not been well constrained due to the lack of suitable minerals for radiometric dating. This paper reports the first SIMS U-Pb age of hydrothermal rutile crystals for the Zhesang Carlin-type gold deposit in the region. The hydrothermal U-bearing rutile associated with gold-bearing sulfides in the deposit yields an U-Pb age of 213.6 ± 5.4 Ma, which is within the range of the previously reported arsenopyrite Re-Os isochron ages (204 ± 19 to 235 ± 33 Ma) for three other Carlin-type gold deposits in the region. Our new and more precise rutile U-Pb age confirms that the gold mineralization was contemporaneous with the Triassic W-Sn mineralization and associated granitic magmatism in the surrounding regions. Based on the temporal correlation, we postulate that coeval granitic plutons may be present at greater depths in the Golden Triangle region and that the formation of the Carlin-type gold deposits is probably linked to the coeval granitic magmatism in the region. This study clearly demonstrates that in situ rutile U-Pb dating is a robust tool for the geochronogical study of hydrothermal deposits that contain hydrothermal rutile.

Nanocrystalline thin films of TiO2 were prepared on glass substrates from an aqueous solution of TiCl3 and NH4OH at room temperature using the simple and cost-effective chemical bath deposition (CBD) method. The influence of deposition time on structural, morphological and optical properties was systematically investigated. TiO2 transition from a mixed anatase-rutile phase to a pure rutile phase was revealed by low-angle XRD and Raman spectroscopy. Rutile phase formation was confirmed by FTIR spectroscopy. Scanning electron micrographs revealed that the multigrain structure of as-deposited TiO2 thin films was completely converted into semi-spherical nanoparticles. Optical studies showed that rutile thin films had a high absorption coefficient and a direct bandgap. The optical bandgap decreased slightly (3.29-3.07 eV) with increasing deposition time. The ease of deposition of rutile thin films at low temperature is useful for the fabrication of extremely thin absorber (ETA) solar cells, dye-sensitized solar cells, and gas sensors.

In this work we report the novel synthesis procedure of phase-pure nano-structured titania in anatase phase using polyacrylamide gel based polymer template method. The evolution of rutile phased titania with increasing temperature has also been investigated. The synthesized nano-materials are characterized using X-ray diffraction, Brunauer - Emmett - Teller surface analysis technique and Scanning electron microscopy. We have used dual phase Rietveld refinement method to analyse the X-Ray diffraction data to get clear picture of crystallographic information of the prepared samples.

We observed the photo-decomposition process of polystyrene latex (PSL) spheres on a rutile TiO2(110) single crystal surface by using atomic force microscopy. During the decomposition process, both the height and width of the PSL spheres linearly decreased with the irradiation time in a similar way from the beginning, suggesting that the PSL spheres are isotropically decomposed. This indicates that the interface between the PSL spheres and the TiO2 surface is not a dominant reaction site, as expected from normal photocatalytic reactions.

Self-powered UV photodetectors based on TiO2 nanotree arrays have captured much attention in recent years because of their many advantages. In this work, rutile/anatase TiO2 (R/A-TiO2 ) heterostructured nanotree arrays are fabricated by assembling anatase nanowires as branches on rutile nanorods. External quantum efficiencies as high as 90% are reached at 325 nm. These high quantum efficiencies are related to the higher amount of light harvesting due to the larger surface area, the better separation ability of the photogenerated carriers by the rutile/anatase heterostructure, and the faster electron transport, related to the 1D nanostructure and lattice connection at the interface of the two kinds of TiO2 . Furthermore, a self-powered wireless UV photodetector is shown with excellent wireless detection performance. Such devices will enable significant advances for next-generation photodetection and photosensing applications.

The Chiapas Massif Complex in the southern Maya terrane is mostly composed of late Permian igneous and meta-igneous rocks. Within this complex in southern Mexico and in the adjacent San Marcos Department of Guatemala, south of the Polochic fault, several small outcrops (~10 km2) of a Phanerozoic andesine anorthosite massif were found following an E-W trend similar to the Polochic-Motagua Fault System. Such anorthosites are related to rutile-bearing ilmenite ore deposits and hornblendite-amphibolite bands (0.1-3 meters thick). The anorthosites show recrystallization and metamorphic retrogression (rutile with titanite rims), but no relicts of high-grade metamorphic minerals such as pyroxene or garnet have been found. In Acacoyagua, Chiapas, anorthosites are spatially related to oxide-apatite rich mafic rocks; in contrast, further to the west in Motozintla, they are related to monzonites. Zircons from these monzonites yield a Permian U-Pb age (271.2×1.4 Ma) by LA-MC-ICPMS. Primary mineral assemblage of the anorthosites include mostly medium to fine-grained plagioclase (>90%) with rutile and apatite as accessory minerals, occasionally with very low amounts of quartz. Massive Fe-Ti oxide lenses up to tens of meters in length and few meters thick are an ubiquitous constituent of these anorthosites and their mineralogy include ilmenite (with exsolution lamellae of Ti-magnetite), rutile, magnetite, clinochlore, ×spinel, ×apatite, ×zircon and srilankite (Ti2ZrO6, first finding of this phase in Mexico). Rutile occurs within the massive ilmenite in two morphological types: (1) fine-grained (5-40 μm) rutile along ilmenite grain boundaries or fractures, and (2) coarse-grained rutile (<5 mm) as discrete grains, whereas magnetite and srilankite only appear as small grains along ilmenite boundaries. Zircon is present as discontinuously aligned small grains (10-40 μm) forming rims around many rutile and ilmenite grains. Attempts to date zircon rims by U-Pb using LA

The adsorption and initial decomposition for methylamine catalyzed by a single Pt atom supported on rutile (110) titania (namely, Pt1/TiO2-R(110)) surface have been investigated by the density functional theory slab calculations with Hubbard corrections (DFT + U). The main purpose of the work is to better understand the role of dispersed platinum metal on the surface of rutile (110) titania in the initial decomposition of methylamine. Our calculated results show that the barriers increased with the order of Csbnd H < Nsbnd H < Csbnd N, which indicates that the Csbnd H bond is the easiest to decompose and the Csbnd N bond is the most difficult to break.

Bone has a built-in electric field because of the presence of piezoelectric collagen. To date, only externally applied electric fields have been used to direct cell behavior; however, these fields are not safe or practical for in vivo use. In this work, for the first time, we use a periodic microscale electric field (MEF) built into a titanium implant to induce osteogenesis. Such a MEF is generated by the periodic organization of a junction made of two parallel semiconducting TiO2 zones: anatase and rutile with lower and higher electron densities, respectively. The junctions were formed through anatase–rutile-phase transition in selective areas using laser irradiation on the implants. The in vitro and in vivo studies confirmed that the built-in MEF was an efficient electrical cue for inducing osteogenic differentiation in the absence of osteogenic supplements and promoted bone regeneration around the implants. Our work opens up a new avenue toward bone repair and regeneration using built-in MEF. PMID:27818718

CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2− anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

Thermochemical cycles consist of a series of chemical reactions to produce hydrogen from water at lower temperatures than by direct thermal decomposition. All the sulfur-based cycles for water splitting employ the sulfuric acid decomposition reaction. This work reports the studies performed on platinum supported on titania (rutile) catalysts to investigate the causes of catalyst deactivation under sulfuric acid decomposition reaction conditions. Samples of 1 wt% Pt/TiO2 (rutile) catalysts were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different times on stream (TOS) between 0 and 548 h. Post-operation analyses of the spent catalyst samples showed that Pt oxidation and sintering occurred under reaction conditions and some Pt was lost by volatilization. Pt loss rate was higher at initial times but total loss appeared to be independent of the gaseous environment. Catalyst activity showed an initial decrease that lasted for about 66 h, followed by a slight recovery of activity between 66 and 102 h TOS, and a period of slower deactivation after 102 h TOS. Catalyst sulfation did not seem to be detrimental to catalyst activity and the activity profile suggested that a complex dynamical situation involving platinum sintering, volatilization, and oxidation, along with TiO2 morphological changes affected catalyst activity in a non-monotonic way.

The role of Al dopant in rutile-phased TiO2 films in the evaluation of the mechanism of leakage current reduction in Al-doped TiO2 (ATO) was studied in detail. The leakage current of the ATO film was strongly affected by the Al concentration at the interface between the ATO film and the RuO2 electrode. The conduction band offset of the interface increased with the increase in the Al dopant concentration in the rutile TiO2, which reduced the leakage current in the voltage region pertinent to the next-generation dynamic random access memory application. However, the Al doping in the anatase TiO2 did not notably increase the conduction band offset even with a higher Al concentration. The detailed analyses of the leakage conduction mechanism based on the quantum mechanical transfer-matrix method showed that Schottky emission and Fowler-Nordheim tunneling was the dominant leakage conduction mechanism in the lower and higher voltage regions, respectively. The chemical analyses using X-ray photoelectron spectroscopy corroborated the electrical test results.

CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2(-) anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process.

Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

The dynamics of a single tripeptide Arg-Gly-Asp (RGD) adsorbing onto negatively charged hydroxylated rutile (110) surface in aqueous solution was studied using molecular dynamics (MD) simulations. The results indicate that the adsorbed Na{sup +} ions play an important role in determining the binding geometry of RGD. With an initial 'horseshoe' configuration, the charged side groups (COO{sup -} and NH{sub 2}) of the peptide are able to interact with the surface through direct hydrogen bonds (H bonds) in the very early stage of adsorption. The Na{sup +} ions approach the positively charged Arg side chain, competing with the Arg side chain for adsorption to the negatively charged hydroxyl oxygen. In coordination with the structural adjustment of the peptide, the Arg residue is driven to detach from the rutile surface. In contrast, the Na+ ions in close proximity to the negatively charged Asp side chain contribute to the binding of the COO{sup -} group on the surface, helping the carboxyl oxygen not involved in COO{sup -}-surface H bonds to orientate toward the hydroxyl hydrogens. Once both carboxyl oxygens form enough H bonds with the hydroxyl hydrogens, the redundant ions move toward a more favorable adsorption site.

Titanium dioxide nanoparticles (nano-TiO2), believed to be inert and safe, are used in many products especially rutile-type in cosmetics. Detection, localization, and count of nanoparticles in tissue sections are of considerable current interest. Here, we evaluate the dose-dependent biodistribution of rutile-type nano-TiO2 exposure during pregnancy on offspring testes. Pregnant mice were subcutaneously injected five times with 0.1 ml of sequentially diluted of nano-TiO2 powder, 35 nm with primary diameter, suspensions (1, 10, 100, or 1,000 μg/ml), and received total doses of 0.5, 5, 50, and 500 μg, respectively. Prior to injection, the size distribution of nano-TiO2 was analyzed by dynamic light scattering measurement. The average diameter was increased in a dose-dependent manner. The most diluted concentration, 1 μg/ml suspension, contained small agglomerates averaging 193.3 ± 5.4 nm in diameter. The offspring testes were examined at 12 weeks postpartum. Individual particle analysis in testicular sections under scanning and transmission electron microscopy enabled us to understand the biodistribution. The correlation between nano-TiO2 doses injected to pregnant mice, and the number of agglomerates in the offspring testes was demonstrated to be dose-dependent by semiquantitative evaluation. However, the agglomerate size was below 200 nm in the testicular sections of all recipient groups, independent from the injected dose during pregnancy.

Antifungal properties of anatase and rutile crystallites isolated from commercial titania P25 photocatalyst were investigated by mycelium growth in the dark and under indoor light. Investigated fungi, i.e., Pseudallescheria boydii, Scedosporium apiospermum, Pseudallescheria ellipsoidea, Scedosporium aurantiacum, Aspergillus versicolor, Aspergillus flavus, Stachybotrys chartarum, Penicillium chrysogenum, Aspergillus melleus, were isolated from air and from moisture condensed on walls. Anatase and rutile were isolated from homogenized P25 (homo-P25) by chemical dissolution, and then purified by washing and thermal treatment. For comparison, homo-P25 was also thermally treated at 200 °C and 500 °C. Titania samples were characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS) and scanning transmission electron microscopy (STEM). It was found that properties of titania, i.e., band-gap energy, impurities adsorbed on the surface, nanoparticle aggregation, and kind of fungal structure, highly influenced resultant antifungal activities. It is proposed that some fungi could uptake necessary water and nutrient from titania surface. It was also found that even when differences in mycelium growth were not significant, the sporulation and mycotoxin generation were highly inhibited by light and presence of titania.

Eclogite mantle xenoliths from the central part of Siberian craton (Udachnaya and Zarnitsa kimberlite pipes) as well as from the northeastern edge of the craton (Obnazhennaya kimberlite) were studied in detail. Garnet and clinopyroxene show evident exsolution textures. Garnet comprises rutile, ilmenite, apatite, and quartz/coesite oriented inclusions. Clinopyroxene contains rutile (± ilmenite) and apatite precipitates. Granular inclusions of quartz in kyanite and garnet usually retain features of their high-pressure origin. According to thermobarometric calculations, the studied eclogitic suite was equilibrated within lithospheric mantle at 3.2-4.9 GPa and 813-1080 °C. The precursor composition of garnets from Udachnaya and Zarnitsa eclogites suggests their stability at depths 210-260 km. Apatite precipitation in clinopyroxenes of Udachnaya and Zarnitsa allows us to declare that original pyroxenes could have been indicative of their high P-T stability. Raman spectroscopic study of quartz and coesite precipitates in garnet porphyroblasts confirms our hypothesis on the origin of the exsolution textures during pressure-temperature decrease. With respect to mineralogical data, we suppose the rocks to be subjected to stepwise decompression and cooling within mantle reservoir.

Angle-resolved photon stimulated desorption (PSD) combined with infrared reflection-adsorption spectroscopy and temperature programmed desorption reveal two distinct channels in the photochemistry of acetone on rutile TiO₂(110) surface. During UV irradiation of co-adsorbed oxygen and acetone molecules, methyl radicals (CH₃) are ejected in two different directions: i) normal to the surface and ii) off-normal at ~±66° to the surface normal in the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti atoms). Both components are relatively narrow and non-cosine, indicating non-thermal evolution of CH₃ radicals. The direction of the “off-normal” PSD component is consistent with orientation of the C–CH₃ bonds in the n²-acetone diolate—a photoactive form of acetone chemisorption on the oxidized TiO₂(110) surface proposed earlier from experimental and theoretical studies. The direction of the “normal” PSD component requires an orientation of a C–CH₃ bond which is not consistent with the n²-acetone diolate structure. The angular distribution of the CH₃ PSD depends on the acetone coverage. The “off-normal” PSD component dominates at lower acetone coverage (< 0.2 ML), but does not increase at higher coverages in accord with the acetone diolate peak intensity in the infrared reflection-absorption spectra. The “normal” PSD component grows with the acetone coverage up to 0.6 ML. The newly discovered “normal” PSD channel is tentatively assigned to a photo-produced n²- acetone enolate as a potential precursor based on the H/D exchange experiments

To magnify anatase/rutile phase junction effects through appropriate Au decorations, a facile solution-based approach was developed to synthesize Au/TiO2 nanoforests with controlled Au locations. The nanoforests cons®isted of anatase nanowires surrounded by radially grown rutile branches, on which Au nanoparticles were deposited with preferred locations controlled by simply altering the order of the fabrication step. The Au-decoration increased the photocatalytic activity under the illumination of either UV or visible light, because of the beneficial effects of either electron trapping or localized surface plasmon resonance (LSPR). Gold nanoparticles located preferably at the interface of anatase/rutile led to a further enhanced photocatalytic activity. The appropriate distributions of Au nanoparticles magnify the beneficial effects arising from the anatase/rutile phase junctions when illuminated by UV light. Under the visible light illumination, the LSPR effect followed by the consecutive electron transfer explains the enhanced photocatalysis. This study provides a facile route to control locations of gold nanoparticles in one-dimensional nanostructured arrays of multiple-phases semiconductors for achieving a further increased photocatalytic activity. PMID:28117448

Rutile titanium dioxide (TiO2) nanostructures were successfully fabricated using the simple chemical bath deposition method at various deposition temperatures. These nanostructures were fabricated on (100 ± 10 nm) TiO2 seed layer coated glass, which was prepared via radio frequency (RF) magnetron sputtering at a substrate temperature of 350 °C. The synthesized TiO2 nanostructures were annealed at 550 °C for 2 h and examined via X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), photoluminescence (PL), and Raman spectroscopy. The XRD patterns showed the presence of the peaks characteristic of rutile phase. The band gap of the TiO2 nanostructures was calculated using the UV-vis absorption spectrum and was determined to be between 3.15 and 3.24 eV. The Raman spectra contained three characteristic bands at 232, 446 and 612 cm-1, which correspond to the tetragonal TiO2 rutile. The results showed good quality of nanocrystalline TiO2 rutile phase.

The mechanisms governing the transport and retention kinetics of titanium dioxide (TiO2, rutile) nanoparticle (NP) aggregates were investigated in saturated porous media. Experiments were carried out under a range of well-controlled ionic strength (from DI water up to 1 mM) and...

The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

Contrary to expectations, the electron transport rate in dye-sensitized solar cells made from single-crystal rutile titanium dioxide nanowires is found to be similar to that measured in dye-sensitized solar cells made from titanium dioxide nanoparticles.

To magnify anatase/rutile phase junction effects through appropriate Au decorations, a facile solution-based approach was developed to synthesize Au/TiO2 nanoforests with controlled Au locations. The nanoforests cons®isted of anatase nanowires surrounded by radially grown rutile branches, on which Au nanoparticles were deposited with preferred locations controlled by simply altering the order of the fabrication step. The Au-decoration increased the photocatalytic activity under the illumination of either UV or visible light, because of the beneficial effects of either electron trapping or localized surface plasmon resonance (LSPR). Gold nanoparticles located preferably at the interface of anatase/rutile led to a further enhanced photocatalytic activity. The appropriate distributions of Au nanoparticles magnify the beneficial effects arising from the anatase/rutile phase junctions when illuminated by UV light. Under the visible light illumination, the LSPR effect followed by the consecutive electron transfer explains the enhanced photocatalysis. This study provides a facile route to control locations of gold nanoparticles in one-dimensional nanostructured arrays of multiple-phases semiconductors for achieving a further increased photocatalytic activity.

To magnify anatase/rutile phase junction effects through appropriate Au decorations, a facile solution-based approach was developed to synthesize Au/TiO2 nanoforests with controlled Au locations. The nanoforests cons®isted of anatase nanowires surrounded by radially grown rutile branches, on which Au nanoparticles were deposited with preferred locations controlled by simply altering the order of the fabrication step. The Au-decoration increased the photocatalytic activity under the illumination of either UV or visible light, because of the beneficial effects of either electron trapping or localized surface plasmon resonance (LSPR). Gold nanoparticles located preferably at the interface of anatase/rutile led to a further enhanced photocatalytic activity. The appropriate distributions of Au nanoparticles magnify the beneficial effects arising from the anatase/rutile phase junctions when illuminated by UV light. Under the visible light illumination, the LSPR effect followed by the consecutive electron transfer explains the enhanced photocatalysis. This study provides a facile route to control locations of gold nanoparticles in one-dimensional nanostructured arrays of multiple-phases semiconductors for achieving a further increased photocatalytic activity.

Au-Cu catalysts supported on anatase or rutile phases were prepared by deposition-precipitation method. The titania polymorph used as the support determined the catalytic behavior. For the Au-Cu/rutile catalysts, the metallic phase had smaller dimensions than for the Au-Cu/anatase catalysts. The catalysts supported on anatase, however, were more active and stable than those supported on rutile. A systematic study of the catalytic activity for CO oxidation as a function of the temperature of activation and the aging time was performed. The catalytic properties were correlated with the properties of the catalysts analyzed with X-ray powder diffraction, refinement of the crystalline structures with the Rietveld method, and transmission electron microscopy. When the support was anatase, a pretreatment at 400 degrees C in air led to the most active catalysts, whereas when the support was rutile, a pretreatment between 200 and 300 degrees C in air led to the most active catalysts; activation under hydrogen generated less active catalysts. The Au-Cu catalysts activated in air were more active for the oxidation of CO than the respective monometallic gold catalysts, indicating a promoting effect between gold and copper to catalyze this reaction.

The performance of phase pure rutile titania nano-particles for gas/vapor sensing is not well explored in open literature, mostly because of their moderate chemical activity. However, the high thermal stability of rutile titania could be beneficial towards making a stable chemi-resistive sensor, operable generally at higher temperature. Herein, we have investigated the chemi-resistive response characteristics of rutile phase titania nano-particles for the detection of isopropanol and formaldehyde vapors. Titania nano-particles are synthesized through a hydrothermal route and characterized in terms of their phase formation behavior and micro-structural features. The sensing characteristics of the particles are measured by varying the operating temperature (275 °C–350 °C) of the sensor and concentrations (20–200 ppm) of the vapors, using a static flow gas sensing measurement set-up. The rutile titania particles are found more responsive towards isopropanol than formaldehyde. An attempt is made here to correlate the sensing performance of titania sensors with the volatility and chemical reactivity of studied vapors. The higher response of the sensor towards isopropanol is predicted, due to its comparatively lower volatility and more suitable chemical structure for oxidation on the sensor surface.

Nanocrystalline TiO 2 powders were prepared by using sol-gel technology. The pH effect on titania phase transformation was investigated from experimental and theoretical approaches. Pure rod-like rutile nanocrystallites formed directly from pH 2 precursor solution. Anatase that formed from pH 4 solution transformed into rutile at the critical size of 9.0 nm, which is much smaller than previously reported (⩾14 nm). Anatase and rutile co-crystallized from the solution of pH 7, while anatase formed from pH 9 solution transformed into rutile at 14.7 nm. Four models of titanium-coordinated complexes were optimized using the density functional theory (DFT/B3LYP) to simulate the structural monomers in different pH solutions. Based on the geometric parameters and Mulliken charge populations calculated, plausible reaction pathways of the titanium-coordinated complexes were anticipated. The theoretical models well explain the experimental results and provide a deep insight into the formation mechanism of different crystal phases at different pH values.

Ti O2 is an oxygen-deficient, intrinsically n -type material, but it is often debated whether the electrons are donated by oxygen vacancies (VO) or titanium interstitials (T ii) . Investigating this issue is complicated by the fact that rutile can self-trap electrons in intrinsic small polaron states, while bulk anatase cannot. The screened hybrid functional HSE06 was proven to account for this phenomenon and has provided quantitatively correct results for VO in our earlier study. Here, we use it for T ii in both rutile and anatase, allowing full spin and symmetry freedom, to shed light on the similarities and differences to VO. We find that these two defects give rise to very similar fingerprints in electron paramagnetic resonance, infrared absorption, or photoelectron spectra. In weakly reduced rutile, the ground state of both defects is (2 +) , with two electrons in polaronic traps, bound loosely to the defect. Most of the time, only these latter states (crudely resembling a hydrogenic series, with increasing distance from the defect) are likely to be detected. In anatase, both VO and T ii can be expected to be ionized at room temperature (singly and doubly, respectively), and the next vertical ionization energy is similar in the two defects—and very close to the ionization energy of the bound polarons in rutile. Most signals in paramagnetic resonance experiments on rutile must also be related to the polaron states, and, in general, very special conditions have to be fulfilled to detect electrons localized to VO or T ii itself. We show that, in thermal equilibrium, the dominant defect in intrinsic samples is VO, and T ii can be the majority defect only in strongly reduced anatase, or in case of p -type doping.

Planewave DFT calculations including ab initio molecular dynamics (AIMD) were used to model the adsorption of a biologically relevant peptide sequence, arginine-glycine-aspartic acid (RGD), upon a rutile TiO2 (110) surface. It was found that binding is solely through the aspartic acid end of the RGD. The carboxy groups bind through dissociative bridging and molecular forms, similar to formic acid. The energy of adsorption is much smaller (0.5-0.77 eV) than seen for formic acid and the molecular adsorption is the strongest adsorption mode. Neutral adsorption is favoured over zwitterionic adsorption and adsorption through the carboxy group of the aspartic acid side chain rather than the terminal carboxy group is favoured due to a configuration allowing an additional surface-carbonyl bond. The RGD backbone is not significantly disrupted upon adsorption.

Density functional theory (DFT) was used to investigate the adsorption of arginine (Arg) on three types of rutile (110) surface [R(110)], i.e., a pristine R(110), an R(110) with two kinds of oxygen deficiency, and an R(110) with an adsorbed water layer. The most stable adsorption configuration on pristine R(110) was identified when the aliphatic straight chain of Arg was parallel to the surface. The hindering effect of in-plane oxygen deficiency is larger than that of bridging oxygen deficiency on the interactions between Arg and R(110). The water layer hinders the Arg adsorption on R(110). These results deepened our understanding of the interfacial interactions between Arg and R(110), and would guide the design and development of tailored biomaterials at the electronic level.

Topical observations of colossal permittivity (CP) with low dielectric loss in donor-acceptor cations co-doped rutile TiO2 have opened up several possibilities in microelectronics and energy-storage devices. Yet, the precise origin of the CP behavior, knowledge of which is essential to empower the device integration suitably, is highly disputed in the literature. From spectromicroscopic approach besides dielectric measurements, we explore that microscopic electronic inhomogeneities along with the nano-scale phase boundaries and the low temperature polaronic relaxation are mostly responsible for such a dielectric behavior, rather than electron-pinned defect-dipoles/grain-boundary effects as usually proposed. Donor-acceptor co-doping results in a controlled carrier-hopping inevitably influencing the dielectric loss while invariably upholding the CP value.

The stable structures of the reconstructed rutile TiO2(011) surface are explored based on an evolutionary method. In addition to the well-known "brookite(001)-like" 2 × 1 reconstruction model, three 2 × 1 reconstruction structures are revealed for the first time, all being more stable in the high Ti-rich condition. Importantly, the predicted Ti4O4-2 × 1 surface model not only is in excellent agreement with the reconstructed metastable surface detected by Tao et al. [Nat. Chem. 3, 296 (2011)] from their STM experiment but also gives a consistent formation mechanism and electronic structures with the measured surface. The computed imaginary part of the dielectric function suggests that the newly predicted reconstructed surfaces are capable of optical absorption over the entire visible light spectrum, thereby offering high potential for photocatalytic applications.

The extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO2. Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

We present a detailed theoretical study of the energetics of stoichiometric steps on the (110) surface of rutile TiO2. Step structures running along the <001>, <111>, and <110> directions including bulk-terminations and possible reconstructions have been considered. A robust method for extracting surface and step energies of vicinal surfaces, where the surface energies converge slowly with respect to slab thickness, is outlined and used. Based on the calculated step energies a 2D Wulff-construction is presented from which it can be concluded that in equilibrium only oxygen terminated steps running along the <001> directions and reconstructed steps along the <111> directions should be present. Finally it is found that under conditions of stoichiometry the reconstructed <111> steps should be more than twice as abundant as oxygen terminated <001> steps.

In this work, bundles of rutile TiO₂ nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO₂-on-CNFs). Morphologies and structures of the TiO₂-on-CNFs are studied using a field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffractometer (XRD) and thermogravimetric analyzer (TGA). Their electrochemical properties as electrodes in lithium ion batteries (LIBs) are investigated and correlated with the morphologies and structures. It is shown that the lateral size of the TiO₂ nanoneedles/nanorods ranges from a few nanometers to tens of nanometers, and increases with the hydrothermal temperature. Small interspaces are observed between individual nanoneedles/nanorods, which are due to the diverging arrangement of nanoneedles/nanorods induced by growing on the convex surface of nanocylinders. It is found that the growth process can be divided into two stages: initial growth on the CNF surface and further growth upon re-nucleation on the TiO₂ bundles formed in the initial growth stage. In order to achieve good electrochemical performance in LIBs, the size of the TiO₂ nanostructures needs to be small enough to ensure complete alloying and fast charge transport, while the further growth stage has to be avoided to realize direct attachment of TiO₂ nanostructures on the CNFs, facilitating electron transport. The sample obtained after hydrothermal treatment at 130 °C for 2 h (TiO₂-130-2) shows the above features and hence exhibits the best cyclability and rate capacity among all samples; the cyclability and rate capacity of TiO₂-130-2 are also superior to those of other rutile TiO₂-based LIB electrodes.

The photocatalytic growth of silver nanoparticles (AgNPs) on rutile TiO2(001) and Fe-modified rutile TiO2(001) monocrystals was investigated. Various amount of Fe was segregated in a controlled way from the doped TiO2 substrates in ultra-high vacuum conditions resulting in low- medium- and high- content of Fe on TiO2 substrates. AgNPs were grown on pristine TiO2 and substrates containing Fe by photoreduction of Ag+ ions under UV illumination. It was found that the size of AgNPs was larger on Fe/TiO2 than on TiO2 while the surface density exhibited the opposite behavior - a large number of AgNPs were present on the TiO2 surface but only a few AgNPs were visible on the Fe/TiO2 substrates. The reason for the differences in size and number of AgNPs on TiO2 and Fe/TiO2 is the limited access of Ag+ to the TiO2 surface caused by the large number of Fe grains segregated onto the TiO2 surface. Another possible reason for the various AgNPs morphologies is alteration in the mechanism of Ag+ photoreduction caused by iron present as Fe3+ ions and by newly formed AgNPs playing the role of electron traps. The surface elemental analysis of the investigated materials was performed with the use of X-ray photoelectron spectroscopy (XPS) and confirmed the composition of AgNPs/Fe/TiO2 systems. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed sizes, morphology and distribution of the nanostructures.

Most of the sample analyzed by the method described were marine muds collected from the Gulf of Maine (Valentine and Commeau, 1990). The silt and clay fraction (up to 99 wt% of the sediment) is composed of clay minerals (chiefly illite-mica and chlorite), silt-size quartz and feldspar, and small crystals (2-12 um) of rutile and hematite. The bulk sediment samples contained an average of 2 to 3 wt percent CaCO3. Tiher samples analyzed include red and gray Carboniferous and Triassic sandstones and siltstones exposed around the Bay of Fundy region and Paleozoic sandstones, siltstones, and shales from northern Maine and New Brunswick. These rocks are probable sources for the fine-grained rutile found in the Gulf of Maine.

The influence of activated carbon (AC) on the photocatalytic activity of different crystalline TiO2 phases was verified in the photocatalytic degradation of methylene blue under UV and solar irradiation. The results showed a volcano trend with a maximum photoactivity for the crystalline phase ratio of anatase:rutile equal to 80:20 both under UV or solar irradiation. By contrast, in presence of AC the photocatalytic activity of the binary materials of TiO2/AC followed an exponential trend, increasing as a function of the increase in anatase proportion in the TiO2 framework. The increase in the photoactivity of the binary material TiO2/AC relative to neat TiO2 was up to 22 and about 17 times higher under UV and visible irradiation, respectively. The present results suggest that AC interacts more efficiently with anatase phase than with rutile phase.

Fine particles of rutile TiO2 supporting nanosized particles of Pt were prepared by a simultaneous in situ sonochemical reduction and deposition method using a standing wave sonochemical reactor (SWSR). The mean diameter of sonochemically obtained Pt particles are of 2 nm. Following this sonochemical technique, rutile TiO2 was also deposited with different weight percentages of Pt. Catalytic function of the prepared composite catalysts were tested by the oxidation of CO to CO(2). From the catalytic activity results, it has been found out that the catalysts prepared by the sonochemical method exhibited higher catalytic activity for CO oxidation, probably attributed to the higher Pt particle distribution achieved under sonication. Transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and diffuse reflectance spectroscopy (DRS) were employed to characterize the resulting material.

The electronic structure of the nanosized rutile TiO2 before and after mechanical lithiation were studied using TEM and EELS. EELS reveals the Li K-edge at the energy-loss position of ~ 61 eV. After lithiation, the separation of the t2g-eg crystal-field splitting on both Ti L2,3-edge and O K-edge decreases, the O K-edge shifts towards a higher energy-loss position and the separation between the pre-edge peak and main peak on the O K-edge decreases. These results suggest that the lithiation of rutile TiO2 was accompanied by the reduction of Ti ion and a charge transfer from Li to Ti.

In this work, tetrakis(dimethylamino)titanium precursor as well as in-situ oxidized ruthenium bottom electrode were used to grow rutile-structured titanium dioxide thin layers by plasma enhanced atomic layer deposition. Metal–insulator–metal capacitors have been elaborated in order to study the electrical properties of the device. It is shown that this process leads to devices exhibiting excellent results in terms of dielectric constant and leakage current.

Luminescence properties of SiO2 in different structural states are compared. Similar comparison is made for GeO2. Rutile and α-quartz structures as well as glassy state of these materials are considered. Main results are that for α-quartz crystals the luminescence of self-trapped exciton is the general phenomenon that is absent in the crystal with rutile structure. In rutile structured SiO2 (stishovite) and GeO2 (argutite) the main luminescence is due to a host material defect existing in as-received (as-grown) samples. The defect luminescence possesses specific two bands, one of which has a slow decay (for SiO2 in the blue and for GeO2, in green range) and another, a fast ultraviolet (UV) band (4.75 eV in SiO2 and at 3 eV in GeO2). In silica and germania glasses, the luminescence of self-trapped exciton coexists with defect luminescence. The latter also contains two bands: one in the visible range and another in the UV range. The defect luminescence of glasses was studied in details during last 60-70 years and is ascribed to oxygen deficient defects. Analogous defect luminescence in the corresponding pure nonirradiated crystals with α-quartz structure is absent. Only irradiation of a α-quartz crystal by energetic electron beam, γ-rays and neutrons provides defect luminescence analogous to glasses and crystals with rutile structure. Therefore, in glassy state the structure containing tetrahedron motifs is responsible for existence of self-trapped excitons and defects in octahedral motifs are responsible for oxygen deficient defects.

Herein, we have fabricated rutile TiO2 nanorod-coupled α-Fe2O3 by a wet-chemical process. It is demonstrated that the visible activities for photoelectrochemical water oxidation and for degrading pollutant of α-Fe2O3 are greatly enhanced after coupling a proper amount of rutile nanorods. The enhanced activity is attributed to the prolonged lifetime and improved separation of photogenerated charges mainly by the transient surface photovoltage responses. Interestingly, the observed EPR signals (with g⊥ = 1.963 and g|| = 1.948) of Ti3+ in the fabricated TiO2-Fe2O3 nanocomposite at ultra low temperature (1.8 k) after visible laser excitation, along with the electrochemical impedance spectra and the normalized photocurrent action spectra, testify evidently that the spacial transfers of visible-excited high-energy electrons of α-Fe2O3 to TiO2 could happen. Moreover, it is confirmed that it is more favorable for the uncommon electron transfers of α-Fe2O3 to rutile than to anatase. This is responsible for the much obvious enhancement of visible activity of Fe2O3 after coupling with rutile TiO2, compared with anatase and phase-mixed P25 ones. This work would help us to deeply understand the uncommon photophysical processes, and also provide a feasible route to improve the photocatalytic performance of visible-response semiconductor photocatalyst for water splitting and pollutant degradation. PMID:25154460

Detailed EPR investigations on as-grown and annealed TiO2 nanoparticles in the anatase and rutile phases were carried out at X-band (9.6 GHz) at 77, 120–300 K and at 236 GHz at 292 K. The analysis of EPR data for as-grown and annealed anatase and rutile samples revealed the presence of several paramagnetic centers: Ti3+, O−, adsorbed oxygen (O2−) and oxygen vacancies. On the other hand, in as-grown rutile samples, there were observed EPR lines due to adsorbed oxygen (O2−) and the Fe3+ ions in both Ti4+ substitutional positions, with and without coupling to an oxygen vacancy in the near neighborhood. Anatase nanoparticles were completely converted to rutile phase when annealed at 1000° C, exhibiting EPR spectra similar to those exhibited by the as-grown rutile nanoparticles. The high-frequency (236 GHz) EPR data on anatase and rutile samples, recorded in the region about g = 2.0 exhibit resolved EPR lines, due to O− and O2− ions enabling determination of their g-values with higher precision, as well as observation of hyperfine sextets due to Mn2+ and Mn4+ ions in anatase. PMID:27041794

To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti0.99Co0.01O2 and ferromagnetic Ti0.95Co0.05O2 films. The Co atoms in the Ti0.99Co0.01O2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO2Ti4 formed around Co in the Ti0.95Co0.05O2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. Asmore » a result, the suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO2.« less

Titanium dioxide (TiO2) bi-phasic powders with individual particles containing an anatase and rutile hetero-junction have been prepared using a sequential layer sol-gel deposition technique to soluble substrates. Sequential thin films of rutile and subsequently anatase TiO2 were deposited onto sodium chloride substrates yielding extremely fragile composite layered discs that fractured into "Janus-like" like powders on substrate dissolution. Nitrogen doped and platinum sputtered analogues were also prepared, and analysed for photocatalytic potential using the photodegradation of Rhodamine B, a model organic pollutant under UV and visible light irradiation. The materials were characterised using X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy and scanning electron microscopy. This paper sheds light on the relationship between anatase and rutile materials when in direct contact and demonstrates a robust method for the synthesis of bi-phasic nanoparticles, ostensibly of any two materials, for photocatalytic reactions or otherwise.

Nitrogen-doped TiO2 materials have been shown to exhibit visible-light photoactivity, but the operative mechanism(s) are not well understood. Here we use structurally and compositionally well-defined epitaxial films of TiO2-xNx anatase (001) and rutile (110) (x≤~0.02) to show a qualitative difference between the visible-light activities for the two polymorphs. Holes generated by visible light at N sites in anatase (001) readily diffuse to the surface and oxidize adsorbed trimethyl acetate while the same in rutile (110) remain trapped in the bulk. In light of the low doping densities that can be achieved in phase-pure material, conventional wisdom suggests that holes should be trapped at N sites in both polymorphs. Although the detailed mechanism is not yet understood, these results suggest that the hole hopping probability is much higher along the [001] direction in N-doped anatase than along the [110] direction in N-doped rutile.

A sample of mineral obtained in the department of Vichada was characterized by the technique of X-ray diffraction in powder samples, in order to determine the crystallographic phases present. After analyzing diffraction patterns, as a result, the mineral had inclusions of Rutile (86.3%) and Manganocolumbita (13.7%). Next, a simulation of the crystal structure of these minerals from the data entered in the databases was carried on. Later, the Rietveld method was used, from this refinement, the new diffraction pattern and the new network parameters were obtained. For the Rutile it was obtained a tetragonal structure, and for the Manganocolumbita an orthorhombic structure was obtained. The characterization is justified among other aspects due to the important applications of these materials in industry and technology, such as Rutile is used in welding rod coatings, in Industries cardboard paper and ink impression among many other uses, the Manganocolumbita is used in special alloys resistant to high temperatures, it also is directly related to the tantalite in coltan formation.

Although the rutile structure of TiO2 is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000 K. In this paper, inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO2 from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizingmore » the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.« less

Titanium dioxide nanoparticles are widely used for photocatalysis, and the relative fraction of titanium dioxide polymorph, i.e. anatase, rutile, or brookite, significantly affects the final performance. Even though conventional phase diagrams indicate a higher stability for the rutile polymorph, it is well established that nanosizes benefit the anatase phase due to its smaller surface energy. However, doping elements are expected to change this behavior, once changes in both surface and bulk energies may occur. Nb2O5 is commonly added to TiO2 to allow property control. However, the effect of niobium on the relative stability of anatase and rutile phases is not well understood from the thermodynamic point of view. The objective of this work was to build a new predictive nanoscale phase diagram for Nb2O5-doped TiO2. Water adsorption microcalorimetry and high temperature oxide melt solution were used to obtain the surface and bulk enthalpies. The phase diagram obtained shows the stable titania polymorph as a function of the composition and size.

To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO{sub 2}, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti{sub 0.99}Co{sub 0.01}O{sub 2} and ferromagnetic Ti{sub 0.95}Co{sub 0.05}O{sub 2} films. The Co atoms in the Ti{sub 0.99}Co{sub 0.01}O{sub 2} simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO{sub 2}Ti{sub 4} formed around Co in the Ti{sub 0.95}Co{sub 0.05}O{sub 2} films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO{sub 2}, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. The suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO{sub 2}.

The wide use of titanium dioxide nanoparticles (TiO2 NPs) in industrial applications requires the investigation of their effects on human health. In this context, we investigated the effects of nanosized and bulk titania in two different crystalline forms (anatase and rutile) in vitro. By colony forming efficiency assay, a dose-dependent reduction of the clonogenic activity of Balb/3T3 mouse fibroblasts was detected in the presence of rutile, but not in the case of anatase NPs. Similarly, the cell transformation assay and the micronucleus test showed that rutile TiO2 NPs were able to induce type-III foci formation in Balb/3T3 cells and appeared to be slightly genotoxic, whereas anatase TiO2 NPs did not induce any significant neoplastic or genotoxic effect. Additionally, we investigated the interaction of TiO2 NPs with Balb/3T3 cells and quantified the in vitro uptake of titania using mass spectrometry. Results showed that the internalization was independent of the crystalline form of TiO2 NPs but size-dependent, as nano-titania were taken up more than their respective bulk materials. In conclusion, we demonstrated that the cytotoxic, neoplastic and genotoxic effects triggered in Balb/3T3 cells by TiO2 NPs depend on the crystalline form of the nanomaterial, whereas the internalization is regulated by the particle size.

The presence of nano-scale lamellae of the alpha-PbO2-type polymorph of TiO2 sandwiched between twinned rutile inclusions in jadeite has been confirmed by electron diffraction and high-resolution transmission electron microscopy, backed up by image simulation techniques, from ultrahigh-pressure jadeite quartzite at Shuanghe in the Dabie Mountains, China. The crystal structure is orthorhombic with lattice parameters a=4.58 A, b=5.42 A, c=5.02 A and space group Pbcn. A three-dimensional structural model has been constructed for the rutile to alpha-PbO2-type TiO2 phase transformation based on high-resolution electron microscopic images. Computer image simulation and structural model analysis reveal that rutile {011}R twin interface is a basic structural unit of alpha-PbO2-type TiO2. Nucleation of alpha-PbO2-type TiO2 lamellae 1-2 nm thick is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure.

TiO2, in the rutile phase with a high concentration of self-doped Ti(3+), has been synthesized via a facile, all inorganic-based, and scalable method of oxidizing TiH2 in H2O2 followed by calcinations in Ar gas. The material was shown to be photoactive in the visible-region of the electromagnetic spectrum. Powdered X-ray diffraction (PXRD), transmission electron microscopy (TEM), ultraviolet-visible-near-infrared (UV-vis-NIR), diffuse reflectance spectroscopy (DRS), and Brunauer-Emmett-Teller (BET) methods were used to characterize the crystalline, structural, and optical properties and specific surface area of the as-synthesized Ti(3+)-doped rutile, respectively. The concentration of Ti(3+) was quantitatively studied by electron paramagnetic resonance (EPR) to be as high as one Ti(3+) per ~4300 Ti(4+). Furthermore, methylene blue (MB) solution and an industry wastewater sample were used to examine the photocatalytic activity of the Ti(3+)-doped TiO2 which was analyzed by UV-vis absorption, Fourier transform infrared spectroscopy (FT-IR), and electrospray ionization mass spectrometry (ESI-MS). In comparison to pristine anatase TiO2, our Ti(3+) self-doped rutile sample exhibited remarkably enhanced visible-light photocatalytic degradation on organic pollutants in water.

The conversion of CO2 by the virtue of sunlight has the great potential to produce useful fuels or valuable chemicals while decreasing CO2 emission from the traditional fossil fuels. Here, we use the first-principles calculations combined with the periodic continuum solvation model (PCSM) to explore the adsorption and reactivity of CO2 on rutile TiO2(110) in the water environment. The results exhibit that both adsorption structures and reactivity of CO2 are greatly affected by water coadsorption on rutile TiO2(110). In particular, the solvation effect can change the most stable adsorption configuration of CO2 and H2O on rutile TiO2(110). In addition, the detailed conversion mechanism of CO2 reduction is further explored in the water environment. The results reveal that the solvation effect cannot only greatly decrease the energy barrier of CO2 reduction but also affect the selectivity of the reaction processes. These results presented here show the importance of the aqueous solution, which should be helpful to understand the detailed reaction processes of photocatalysts.

In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, {sup 1}H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO{sub 2} under visible light ({lambda}>420 nm). These hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity. - Graphical abstract: Hierarchical chlorine-doped rutile TiO{sub 2} spherical clusters of nanorods photocatalyst were synthesized on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light ({lambda}>420 nm)

The nucleation and growth of Pt nanoparticles (NP’s) on rutile TiO{sub 2} (110) surfaces with O on-top atoms (oxidized TiO{sub 2}), surface O vacancies, and H adatoms, respectively (reduced TiO{sub 2}), was studied by means of scanning tunneling microscopy (STM) experiments and density functional theory calculations. At room temperature, Pt was found to be trapped at O on-top atoms and surface O vacancies, leading to rather small Pt NP’s. In contrast, on surfaces with H adatoms the mobility of Pt was much larger. As a result, large Pt NP's were found at room temperature on TiO{sub 2} (110) surfaces with H adatoms. However, at ∼150 K the diffusion of Pt was kinetically hindered on all TiO{sub 2} (110) surfaces considered. STM data acquired after vacuum-annealing at 800 K showed comparable results on all TiO{sub 2} (110) surfaces because the diffusion of Pt is not influenced by surface defects at such high temperatures.

Despite the rising technological interest in the use of calcium-modified TiO2 surfaces in biomedical implants, the Ca/TiO2 interface has not been studied in an aqueous environment. This investigation is the first report on the use of in situ scanning tunneling microscopy (STM) to study calcium-modified rutile TiO2(110) surfaces immersed in high purity water. The TiO2 surface was prepared under ultrahigh vacuum (UHV) with repeated sputtering/annealing cycles. Low energy electron diffraction (LEED) analysis shows a pattern typical for the surface segregation of calcium, which is present as an impurity on the TiO2 bulk. In situ STM images of the surface in bulk water exhibit one-dimensional rows of segregated calcium regularly aligned with the [001] crystal direction. The in situ-characterized morphology and structure of this Ca-modified TiO2 surface are discussed and compared with UHV-STM results from the literature. Prolonged immersion (two days) in the liquid leads to degradation of the overlayer, resulting in a disordered surface. X-ray photoelectron spectroscopy, performed after immersion in water, confirms the presence of calcium.

Inulin, a water soluble carbohydrate polymer, was extracted from Allium sativum L. by hot water diffusion method. A novel bio-nanocomposite was prepared by embedding TiO2 (rutile) onto the inulin matrix. The extracted inulin and the prepared bio-nanocomposite were characterized using UV-vis, FT-IR, XRD, SEM, TEM and TGA techniques. The photocatalytic activity of the bio-nanocomposite for the degradation of methylene blue was studied under UV illumination in batch mode experiment and was found to be twice as high as that of pristine TiO2. The kapp for inulin-TiO2 (0.0449 min(-1)) was higher than that for TiO2 (0.0325 min(-1)) which may be due to the synergistic action of inulin and TiO2. The stabilization of photo excited electron suppressed the electron-hole pair recombination thereby inducing the electrons and the holes to participate in the photo reduction and oxidation processes, respectively and enhancing the photocatalytic activity.

Carbon-coated rutile titanium dioxide (CRT) was fabricated through an in-situ pyrolysis of titanium-based metal organic framework (Ti8O8(OH)4[O2CC6H4CO2]6) crystals. Benefiting from the Tisbnd Osbnd C skeleton structure of titanium-based metal organic framework, the CRT possesses abundant channels and micro/mesopores with the diameters ranging from 1.06 to 4.14 nm, shows larger specific surface area (245 m2 g-1) and better electronic conductivity compared with pure titanium dioxide (12.8 m2 g-1). When applied as anode material for sodium-ion batteries, the CRT electrode exhibits a high cycling performance with a reversible capacity of ∼175 mAh g-1 at 0.5 C-rate after 200 cycles, and obtains an excellent rate capability of ∼70 mAh g-1 after 2000 cycles even at a specific current of 3360 mA g-1(20 C-rate). The outstanding rate capability can be attributed to the carbon-coated structure, which may effectively prevent aggregation of the titanium dioxide nanoparticles, accelerate the mass transfer of Na+ and speed up the charge transfer rate. Considering these advantages of this particular framework structure, the CRT can serve as an alternative anode material for the industrial application of SIBs.

There has been a great interest in preparing both rutile (R) and anatase (A) forms of TiO2 films for various optical, electrical, photocatalysis, photovoltaics, and biosensor applications. The R-TiO2 is superior in optical properties and thermodynamically more stable than A-TiO_2. However, the latter has attracted much attention recently as the most promising photocatalytic material. In general, the formation of R-phase of TiO2 films requires a higher substrate temperature (> 300 ^circC), whereas a lower substrate temperature results in either A-phase or an amorphous structure. In the present work, we have prepared A- and R-TiO2 films ( ~ 500 nm thick) on unheated glass substrates by RF magnetron sputtering by controlling the total pressure of sputtering gases (Ar + O_2). The crystal structures of the films were confirmed by x-ray diffraction and Raman scattering. The analysis of optical transmission and reflection data measured in the UV-Visible region (175 nm- 2500 nm) show an optical bandgap of ~ 3.1 eV (direct) for R-phase, and ~ 3.2 eV (indirect) for A-phase of TiO2 films.

Quasielastic neutron scattering (QENS) was used to investigate the diffusion dynamics of hydration water on the surface of rutile (TiO{sub 2}) nanopowder. The dynamics measurements utilizing two inelastic instruments, a backscattering spectrometer and a disk chopper spectrometer, probed the fast, intermediate, and slow motions of the water molecules on the time scale of picoseconds to more than a nanosecond. We employed a model-independent analysis of the data collected at each value of the scattering momentum transfer to investigate the temperature dependence of several diffusion components. All of the probed components were present in the studied temperature range of 230-320 K, providing, at a first sight, no evidence of discontinuity in the hydration water dynamics. However, a qualitative change in the elastic scattering between 240 and 250 K suggested a surface freezing-melting transition, when the motions that were localized at lower temperatures became delocalized at higher temperatures. On the basis of our previous molecular dynamics simulations of this system, we argue that interpretation of QENS data from such a complex interfacial system requires at least qualitative input from simulations, particularly when comparing results from spectrometers with very different energy resolutions and dynamic ranges.

Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1×1 surface reveal several distinct reaction channels in a temperature range of 50 – 500 K. NO readily reacts on TiO2(110) to form N2O which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a byproduct of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa’s and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction productmore » desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Hierarchical TiO(2) nanostructures would be desirable for preparing dye-sensitized solar cells because of their large amount of dye adsorption and superior light harvesting efficiency, as well as efficient charge separation and transport properties. In this study, rutile TiO(2) nano-branched arrays grown directly on transparent conductive glass (FTO) were prepared by a facile two-step wet chemical synthesis process, using a simple aqueous chemical growth method involving immersing the TiO(2) nanorod arrays in an aqueous TiCl(4) solution as seeds, which were prepared by a hydrothermal method. The dye-sensitized solar cells based on the TiO(2) nano-branched arrays which were only about 3 μm in length show a short-circuit current intensity of 10.05 mA cm(-2) and a light-to-electricity conversion efficiency of 3.75%, which is nearly three times as high as that of bare nanorod arrays, due to the preferable nanostructure, which not only retains the efficient charge separation and transport properties of the nanorod arrays, but also can improve the amount of dye adsorption due to the increased specific surface area from the nanobranches.

Spectroscopic ellipsometry at room temperature is applied in order to determine the ordinary (ε{sub ⊥}) and extraordinary (ε{sub ∥}) dielectric functions (DFs) of rutile SnO{sub 2} corresponding to electric field (E) polarization perpendicular (E⊥c) and parallel (E∥c) to the optical axis (c), respectively. Strong anisotropic behavior is found for the full spectral range from 0.5 up to 20 eV. The onsets of strong absorption are found at 4.28 eV and 5.42 eV for E⊥c and E∥c, respectively. A dipole-forbidden band gap at (3.59 ± 0.2) eV at room temperature is found by line shape fits to the imaginary parts of the DFs. Further high-energy transitions are resolved. Their accurate energy values are obtained by fitting the second derivatives of the DFs. Comparison to published DFs calculated by ab-initio theory demonstrates that the electron-hole interaction in SnO{sub 2} is strong and has to be included for interpretation.

The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formed in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .

We have performed non-equilibrium molecular dynamics simulations of various TiO2/water interfaces at ambient temperature in presence of oscillating electric fields in frequency range 20-100 GHz and RMS intensities 0.05-0.25 V/Å. Although the externally applied fields are by one order of magnitude lower than the intrinsic electric field present on the interfaces (˜1.5-4.5 V/Å), significant non-thermal coupling of rotational and translational motion of water molecules was clearly observed. Enhancement of the motion, manifested by increase of diffusivity, was detected in the first hydration layer, which is known to be heavily confined by adsorption to the TiO2 surface. Interestingly, the diffusivity increases more rapidly on anatase than on rutile facets where the adsorbed water was found to be more organized and restrained. We observed that the applied oscillating field reduces number of hydrogen bonds on the interface. The remaining H-bonds are weaker than those detected under zero-field conditions; however, their lifetime increases on most of the surfaces when the low-frequency fields are applied. Reduction of adsorption interaction was observed also in IR spectra of interfacial water where the directional patterns are smeared as the intensities of applied fields increase.

TiO2 is a best choice of electron transport layers in perovskite solar cells, due to its high electron mobility and stability. However, traditional TiO2 processing method requires rather high annealing temperature (>500 °C), preventing it from application to flexible devices. Here, we show that TiO2 thin films can be synthesized via chemical bath deposition below 100 °C. Typically, a compact layer of rutile TiO2 is deposited onto fluorine-doped tin oxide (FTO) coated substrates, in an aqueous TiCl4 solution at 70 °C. Through the optimization of precursor concentration and ultraviolet-ozone surface modification, over 12% power conversion efficiency can be achieved for CH3NH3PbI3 based perovskite solar cells. These findings offer a potential low-temperature technical solution in using TiO2 thin film as an effective transport layer for flexible perovskite solar cells.

The associative and dissociative adsorption of water molecules at low-coverage situations on rutile TiO2 (110) surface with step defects was investigated by the density functional theory calculations. Structural optimization of the hydroxylated/hydrated configurations at step edges along the crystal directions and the dynamic process of water dissociation were discussed to get a better description of the water/TiO2 interface. Our results indicate that steps on the TiO2 (110) surface could be an active site for water dissociation. The results of geometry optimization suggest that the stability of hydroxylated configuration is largely dependent on the locations of the H species and the recombination of water molecules from hydroxyls is observed in the fully hydroxylated condition. However, these hydroxyls can be stabilized by the associatively absorbed water nearby by forming competitive intermolecular hydrogen bonds. The dynamics of water dissociation and hydrogen diffusion were studied by the first principles molecular dynamics simulation and our results suggest that the hydrogen released by water dissociation can be transferred among the adsorbates, such as the unsaturated oxygen atoms-H2O-hydroxyl (TiO-H2O-OH) complex at step edges, or gradually diffuses to the bulk water system in the form of hydronium (H3O+) at higher water coverage.

Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50-500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

Adsorption and photodecomposition of formic acid on rutile TiO{sub 2} (110) have been investigated with infrared reflection–absorption spectroscopy (IRRAS) employing p- and s-polarized light along the [001] and [11{sup ¯}0] crystal directions. The single crystal surfaces were prepared either by sputtering and annealing in ultrahigh vacuum (UHV) to obtain a reduced surface (r-TiO{sub 2}), or by sputtering without annealing to create a rough, highly defective surface (sp-TiO{sub 2}). Results are compared with corresponding measurements on rutile nanocrystals performed in synthetic air. IRRAS spectra obtained on r-TiO{sub 2} and rutile nanocrystals are very similar, and show that in both cases formic acid dissociates and is predominately adsorbed as a bridging bidentate formate species, and that the formate adsorption structure on the nanocrystals is dominated by interactions with majority (110) surfaces. In contrast, the IRRAS spectra on sp-TiO{sub 2} are different, with only minor spectral features associated with (110) surfaces and lost azimuthal symmetry, both of which imply changed adsorption geometry due to bonding to low-coordinated Ti atoms with lower valences. The UV-induced rate of formate photodecomposition is about 30 times higher on rutile nanocrystals in synthetic air compared with sp-TiO{sub 2} under UHV conditions, and even larger than on r-TiO{sub 2}. These differences are explained by the lack of oxygen and limited hydroxyl coverage under UHV conditions. The difference in reactivity between the r-TiO{sub 2} and sp-TiO{sub 2} surfaces is attributed to a high concentration of strongly bonded bridging bidentate formate species on the (110) surface, which lowers its reactivity. The results point to a pressure gap where the availability of molecular oxygen and the hydroxyl concentration limit the photoreactivity in UHV leading to an almost 20-fold decrease of the formate degradation rate in UHV. In contrast, the structure represented by the single

Traditionally, we use a slab to mimic a surface and we constrain the slab to have the bulk-terminated 2D lattice constants. Here we propose a different model in which we impose no constraints, allowing all coordinates including the 2D slab itself to relax. We perform DFT calculations on both models. We find that the unconstrained slabs yield better agreement with experimental results and they have lower total energies. The optimized 2D lattice constants of the unconstrained slabs eventually converge to the attached bulk value. The total energy difference reveals that, with odd number trilayers, the unconstrained slab is much closer to the corresponding constrained slab. The surface energies both converge to the individual values with the number of atomic layers. Project supported in part by the Major Program of National Science Foundation of China (No. 51090385) and the National Natural Science Foundation of China (No. 50974067).

While geo- and thermo-chronology of detrital minerals from sedimentary basins are routinely applied to constrain sedimentary provenance and hinterland evolution, the importance of a multi-technique approach is not always recognized. Isotopic dating methods sensitive to different temperature ranges can be successfully applied to detrital mineral grains from the same sample in order to obtain a robust dataset capable of providing information on the various thermal events that affected the source terrains. We use three detrital minerals in this study (zircon, rutile and white mica) that are stable and widely distributed in igneous, metamorphic and sedimentary rocks and which together retain source crystallisation and cooling information over the range down to ~200°C and thus record complex metamorphic histories. Similarly to zircon and other U-bearing minerals, rutile can be dated by the U-Pb method, however it has so far received less attention than zircon because of: lower U content which limits measurement quality by in situ methods, often a higher proportion of common (non radiogenic) lead, and a lack of widely available good quality reference materials. We have recently characterized (by high precision ID-TIMS, isotope dilution mass spectrometry, and by LA-MC-ICP-MS two natural rutiles (Sugluk-4 and PCA-S207) and used these as reference materials for LA U-Pb dating of detrital samples, Parrish et al., this meeting, and [1]). Compared to zircon, rutile is characterized by a lower closure T for Pb diffusion (~500°C), hence rutile U-Pb dates primarily indicate the time since the last significant cooling. As it adds an important lower temperature complement to zircon and allows a much more unique isotopic fingerprint of the source region, rutile has the potential to become a key provenance tracer. In order to boost the strength of the double U-Pb detrital chronometer, we apply 40Ar/39Ar dating and zircon fission track dating to detrital grains from the same sample

The same Bragg reflection in TiO2 from twelve different CBED patterns (from different crystals, orientations and thicknesses) are analysed quantitatively in order to evaluate the consistency of the QCBED method for bond-charge mapping. The standard deviation in the resulting distribution of derived X-ray structure factors is found to be an order of magnitude smaller than that in conventional X-ray work, and the standard error (0.026% for FX(110)) is slightly better than obtained by the X-ray Pendellosung method applied to silicon. This is sufficiently accuracy to distinguish between atomic, covalent and ionic models of bonding. We describe the importance of extractingmore » experimental parameters from CCD camera characterization, and of surface oxidation and crystal shape. Thus, the current experiments show that the QCBED method is now a robust and powerful tool for low order structure factor measurement, which does not suffer from the large extinction (multiple scattering) errors which occur in inorganic X-ray crystallography, and may be applied to nanocrystals. Our results will be used to understand the role of d electrons in the chemical bonding of TiO2.« less

We report molecular dynamics (MD) simulations of the water/clean rutile TiO2 (110) interface using polarizable and non-surface polarity force field models. The effect of surface polarity on the water dynamics near the TiO2(110) surface is addressed, specifically by calculating the water hydrogen bond and reorientational dynamics. The hydrogen bond lifetime of interfacial water molecules is several times longer than that of bulk water due to the strong water-TiO2 interactions. A comparison of the dynamics simulated with the polarizable and non-surface polarity models shows that, while the hydrogen bond lifetime between the interfacial water and TiO2 surface is insensitive to the surface polarity, the reorientational dynamics around this hydrogen bond axis is significantly influenced by the surface polarity; the surface polarity of the TiO2 increases the water-TiO2 interactions, stabilizing the local structure of the interfacial water molecules and restricting their rotational motion. This reorientation occurs predominantly by rotation around the O-H group hydrogen bonded to the TiO2 surface. Furthermore, we correlate the dynamics of the induced charge on the TiO2 surface with the interfacial water dynamics. Our results show that the timescale of correlations of the atom charges induced by the local electric field in bulk water is influenced by the rotational motion, hydrogen bond rearrangement and translational motion, while the induced charge dynamics of the TiO2 surface is governed primarily by the rotational dynamics of the interfacial water molecules. This study demonstrates that the solid surface polarity has a significant impact on the dynamics of water molecules near TiO2 surfaces.

We model rutile titanium dioxide nanocrystals (NCs) up to ˜1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.

In reduced TiO2, electronic transitions originating from the Ti(3+)-induced states in the band gap are known to contribute to the photoabsorption, being in fact responsible for the material's blue color, but the excited states accessed by these transitions have not been characterized in detail. In this work we investigate the excited state electronic structure of the prototypical rutile TiO2(110) surface using two-photon photoemission spectroscopy (2PPE) and density functional theory (DFT) calculations. Using 2PPE, an excited resonant state derived from Ti(3+) species is identified at 2.5 ± 0.2 eV above the Fermi level (EF) on both the reduced and hydroxylated surfaces. DFT calculations reveal that this excited state is closely related to the gap state at ∼1.0 eV below EF, as they both result from the Jahn-Teller induced splitting of the 3d orbitals of Ti(3+) ions in reduced TiO2. Localized excitation of Ti(3+) ions via 3d → 3d transitions from the gap state to this empty resonant state significantly increases the TiO2 photoabsorption and extends the absorbance to the visible region, consistent with the observed enhancement of the visible light induced photocatalytic activity of TiO2 through Ti(3+) self-doping. Our work reveals the physical origin of the Ti(3+) related photoabsorption and visible light photocatalytic activity in prototypical TiO2 and also paves the way for the investigation of the electronic structure and photoabsorption of other metal oxides.

The structure solution of the modulated, delafossite-related, orthorhombic Ga3-xIn3TixO9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A3-xIn3TixO9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga1.5In3Ti1.5O9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga3-xIn3TixO9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ∼3.4 eV before a ∼0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ∼3.0 eV. Resistance to oxidation and reduction is also presented.

Nanoparticles of basic composition Sn1-xCoxO2 (x=0.00, 0.01, 0.03, 0.05 and 0.1) were synthesized through the citrate-gel method and were characterized for structural properties using X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FT-IR). XRD analysis of the powder samples sintered at 500 °C for 12 h showed single phase rutile type tetragonal structure and the crystallite size decreased as the cobalt content was increased. FT-IR spectrum displayed various bands that came due to fundamental overtones and combination of O-H, Sn-O and Sn-O-Sn entities. The effect of Co doping on the electrical and magnetic properties was studied using dielectric spectroscopy and vibrating sample magnetometer (VSM) at room temperature. The dielectric parameters (ε, tan δ and σac) show their maximum value for 10% Co doping. The dielectric loss shows anomalous behavior with frequency where it exhibits the Debye relaxation. The variation of dielectric properties and ac conductivity with frequency reveals that the dispersion is due to the Maxwell-Wagner type of interfacial polarization in general and hopping of charge between Sn2+ and Sn4+ as well as between Co2+ and Co3+ ions. The complex impedance analysis was used to separate the grain and grain boundary contributions in the system which shows that the conduction process in grown nanoparticles takes place predominantly through grain boundary volume. Hysteresis loops were observed clearly in M-H curves from 0.01 to 0.1% Co doped SnO2 samples. The saturation magnetization of the doped samples increased slightly with increase of Co concentration. However pure SnO2 displayed paramagnetism which vanished at higher values of magnetic field.

The electronic and magnetic properties of double-impurities-doped SnO{sub 2} (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn{sub 1-2x}Cr{sub x}Mn{sub x}O2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μ{sub B} per supercell. The Cr-and Mn-doped SnO{sub 2} system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO{sub 2}, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO{sub 2}. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

Novel g-C3N4/rutile-brookite TiO2-xNy composite photocatalysts were fabricated through a facile solvothermal approach. The effect of rutile phase TiO2 with brookite TiO2 and g-C3N4 on the photocatalytic activity of g-C3N4/nitrogen-doped TiO2 composite was studied. The photocatalytic performance of the photocatalyst was evaluated by measuring the degradation of NO gas under visible and UV light irradiation. It is suggested that g-C3N4/rutile-brookite TiO2-xNy forms a Z-scheme photocatalytic system, which shows improvement on the photocatalytic activity than that of g-C3N4/single brookite TiO2-xNy. By importing rutile phase TiO2-xNy, the photogenerated electrons can efficiently transfer from rutile TiO2 to g-C3N4, which results in the separation of electron and hole pairs, enhancing the photocatalytic ability. However, single brookite TiO2-xNy can not remove the photogenerated electrons efficiently and the photocatalytic performances of composites decrease with g-C3N4 amount increase.

Deposits of minerals containing niobium (columbium), thorium, and rare earths occur in the Mineral Hill district, 30 miles northwest of Salmon, Lemhi County, Idaho. Monazite, thorite, allanite, and niobium-bearing rutile form deposits in metamorphic limestone layers less than 8 feet thick. The known deposits are small, irregular, and typically located in or near small folds. Minor faults are common. Monazite generally is coarsely crystalline and contains less than one percent thorium. Rutile forms massive lumps up to 3 inches across; it contains between 5 and 10 percent niobium. Rutile occurs in the northwestern half of the district, thorite in the central and southeastern parts. Monazite occurs in all deposits. Allanite is locally abundant and contains several percent thorium. Magnetite and ilmenite are also locally abundant. A major thrust fault trending northwest across the map-area separates moderately folded quartzite and phyllitic rocks of Belt age, on the northeast, from more intensely metamorphosed and folded rocks on the southwest. The more metamorphosed rocks include amphibolite, porphyroblastic feldspar gneiss, quartzite, and limestone, all probably of sedimentary origin, and probably also of Belt (late Precambrian) age. The only rocks of definite igneous origin are rhyolite dikes of probable Tertiary age. The more metamorphosed rocks were formed by metasomatic metamorphism acting on clastic sediments, probably of Belt age, although they may be older than Belt. Metamorphism doubtless was part of the episode of emplacement of the Idaho batholith, but the history of that episode is not well understood. The rare-element deposits show no evidence of fracture-controlled hydrothermal introduction, such as special fracture systems, veining, and gangue material. They may, however, be of hydrothermal type. More likely they are metamorphic segregations or secretions, deposited in favorable stratigraphic and structural positions during regional metamorphism.

A low temperature approach was developed for the deposition of rutile TiO2 particles on a wood surface by hydrolysis of TiCl4 in aqueous solutions acidified with HCl, and crystallization at 75 and 90 °C (1 h). Prior to hydrothermal treatment, Picea Abies wood was first soaked in a 0.5 mmol/l aqueous solution containing anionic surfactant sodium dodecyl sulphate (SDS, Sigma Aldrich) for 2 h at 80 °C. The crystal structure of the hydrothermally made rutile particles was determined with XRD, while the morphology of the deposited TiO2 particles and their distribution in the wood were examined with SEM and EDX measurements. The penetration and amount of deposited rutile particles could be modified by changing the deposition conditions. Thicker layers were obtained from more concentrated aqueous TiCl4 solutions with and without added HCl, and with longer deposition times and higher temperatures of the hydrothermal treatment. The interaction of TiO2 particles with hemicellulose and lignin in wood was established from infrared attenuated total reflection (FT-IR ATR) and Raman spectra measurements, from which the spectra of wood were subtracted. Analysis of the subtraction spectra showed the presence of titania particles on the wood surface, revealing also the establishment of TiO2-wood coordinative bonds of titanium ions with hemicellulose and lignin. The red frequency shift of the OH stretching modes suggested interaction of the TiO2 particles with water molecules of wood. TiO2 deposited on wood treated with SDS became hydrophobic (water contact angles (WCA) of 150°), contrasting the properties of untreated wood with a deposited TiO2 particle coating, which remained hydrophilic.

Garnet ages for the Lowlands range from 1,168-1,127 Ma, those from the central and southern Highlands from 1,154-1,013 Ma. Metamorphism in the Highlands may not have occurred as a single event but rather in several discrete thermal pulses. An age of 1,153 {plus minus} 3 Ma was determined for garnets in the syn-regional metamorphic contact aureole of the Diana syenite, consistent with that of the syenite intrusion, 1 155 {plus minus} 4 Ma. Garnets just outside the contact aureole give an age of 1,168 {plus minus} 6 Ma. In the Lowlands, monazite yielded an age of 1,161 {plus minus} 1 Ma, rutiles yielded ages of 1,005 {plus minus} 2 Ma and 953 {plus minus} 4 Ma, and sphene ages range from 1,156 to 1,103 Ma. In the Highlands, monazite yielded an age of 1,033 {plus minus} 1 Ma, rutiles yielded ages of 911 {plus minus} 2 Ma and 885 {plus minus} 2 and sphenes from 1,033 Ma to 991 Ma. The rutile and monazite ages indicate that both terranes cooled at time-integrated rates of ca. 1.5C/Ma for at least 150 Ma following the last phase of high-grade metamorphism. The Lowlands cooled to ca. 400C by ca. 1,000 Ma and the Highlands by ca. 900 Ma. The mineral ages indicate that metamorphic pressures and temperatures recorded by thermobarometry correspond to conditions attained polychronically over 150 Ma or more. Mineral ages combined with temperature estimates for peak metamorphism indicate that the closure temperature for the U-Pb system is >800C in garnet, 640-730C in monazite, and 500-670C in sphene.

Titanium dioxide (TiO2) nanoparticles were grown using nanosecond pulsed laser ablation of Ti target in DI water and in 0.001 M sodium dodecyl sulfate (SDS) surfactant aqueous solution. Growth was carried out with varying ablation times i. e. 30 min, 60 min and 90 min. The objective of our study was to investigate the influence of variations in liquid ambience conditions on the growth of the nanoparticles in a pulsed laser ablation in liquid (PLAL) process. Size, composition and optical properties of the grown TiO2 nanoparticles were investigated using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), optical absorption, photoluminescence (PL) spectroscopy and X-ray diffraction (XRD) studies. The obtained nanoparticles of TiO2 were found almost spherical in shape and polycrystalline in nature in both the liquid mediums i.e. DI water and aqueous solution of surfactant. Nanoparticles number density was also found to increase with increasing ablation time in both the liquid mediums. However crystalline phase of the grown TiO2 nanoparticles differs with the change in liquid ambience conditions. Selected area electron diffraction (SAED), PL and XRD studies suggest that DI water ambience is favorable for the growth of anatase phase TiO2 nanoparticles for all ablation times. While Surfactant added water ambience is favorable for the growth of rutile phase TiO2 nanoparticles but for shorter ablation times of 30 min and 60 min only, for longer ablation time of 90 min anatase phase was also observed along with the rutile phase TiO2 nanoparticles. The formation of anatase phase in DI water and rutile and anatase phase in aqueous solution of surfactant is explained on the basis of varying thermodynamic conditions with the two different liquid ambiences and different ablation times.

The solubility of rutile in water-saturated haplogranite melts with molar Al/(Na + K)-ratios ranging from 0.84 to 1.25 was determined at 750-900 °C and 2 kbar in cold-seal pressure vessel experiments. Due to the low diffusivity of Ti at these conditions a new method was developed to determine TiO2 solubility. In this method, glasses with TiO2 gradients were used as starting material, and after the experiments the TiO2 content was measured at the contact between rutile-bearing and rutile-free glass. The glasses were either directly equilibrated at the desired P-T conditions (i.e., crystallization experiments), or first treated at 50-150 °C lower temperatures and then subjected to the desired conditions (i.e., dissolution experiments). The results obtained in crystallization and dissolution experiments agree well with each other, suggesting that equilibrium was attained. Rutile solubility in peralkaline melts strongly increases with temperature and the amount of excess alkalies according to the relation: log TiO2 (wt%)=(1.8∗ΔANK-0.53)∗10,000/T-(12.8∗ΔANK-4.3) in which ΔANK is the deviation of the molar Al/(Na + K)-ratio from unity and T is given in Kelvin. Excess alumina does not seem to promote TiO2 solubility. For natural melt compositions it was found that if Ca, Mg and Fe are assumed to be 10 times less effective in promoting TiO2 solubility than excess Na and K, good fits to previous solubility data in silicic (⩾70 wt% SiO2) melts at upper crustal pressures (⩽10 kbar) are obtained. Application of this extended TiO2 solubility model to natural melt inclusions in quartz phenocrysts from five silicic volcanic systems returns TiO2 activities that are similar to those calculated with a previous experiment-based model and to those calculated from pairs of coexisting Fe-Ti-oxides, but are up to 2.9 times higher than those calculated with MELTS and rhyolite-MELTS. Pressures calculated from Ti concentrations in the host quartz using the most recent

The rutile TiO2 nanorods (RTNs) with the length of 40-130 nm and diameters approximately 8-15 nm, containing some 300-500 nm sized RTN aggregates and 6% of anatase TiO2 nanocrystals, were prepared by surfactant-assisted hydrothermal method. The dye-sensitized solar cell (DSC) based on the RTNs exhibited power conversion efficiency of 6.03%. As compared to P25 TiO2 based DSC, RTNs based DSC shows improved light-harvesting and Brunauer-Emmett-Teller surface area, leading to an increase in short-circuit current (Jsc) by 40.6%.

TiO2 is a semiconducting material that has been used extensively in many industrial applications, and recently has become a candidate for photocatalytic water splitting, fuel cell anode support materials, sensors, and other novel nanodevices. The interface of TiO2 with water, historically well-studied but still poorly understood, presents a ubiquitous environmental challenge towards the ultimate practical usefulness of these technologies. Ground-state density functional theory (DFT) calculations studying the characteristics of molecular adsorption on model surfaces have been studied for decades, showing constant improvement in the description of the energetics and electronic structure at interfaces. These simulations are invaluable in the materials science innovation pipeline because they can interpret the results of experiments and investigate properties at the nanoscale that traditional methods cannot reach. In this work, spin-polarized DFT calculations within the generalized gradient approximation and with the recent self-consistent opt-B88 van der Waals functional have been applied to investigate the problem of molecularly adsorbed water on the rutile (110) TiO2 surface under the influence of an applied electric field. The effective screening medium theory is used to break the symmetry of the simulation in the slab normal direction and implement a metal-like boundary condition at the edges of the simulation cell to model the charged capacitor in a real electrochemical device. This study begins with an investigation of bulk and surface properties of TiO2 to obtain a sound theoretical baseline. Following that, an attempt to obtain simple and meaningful structure-property relationships of rectangular TiO 2 nanowires with (110) facets resulting from quantum confinement. Finally, a systematic study of energetics, geometrical configuration, charge partitioning, and electronic structure of water in monomer coverage up to monolayer coverage provides insight into the

The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

In this paper, we investigated the dielectric properties of (In + Nb) co-doped rutile TiO2 single crystal and polycrystalline ceramics. Both of them showed colossal, up to 104, dielectric permittivity at room temperature. The single crystal sample showed one dielectric relaxation process with a large dielectric loss. The voltage-dependence of dielectric permittivity and the impedance spectrum suggest that the high dielectric permittivity of single crystal originated from the surface barrier layer capacitor (SBLC). The impedance spectroscopy at different temperature confirmed that the (In + Nb) co-doped rutile TiO2 polycrystalline ceramic had semiconductor grains and insulating grain boundaries, and that the activation energies were calculated to be 0.052 eV and 0.35 eV for grain and grain boundary, respectively. The dielectric behavior and impedance spectrum of the polycrystalline ceramic sample indicated that the internal barrier layer capacitor (IBLC) mode made a major contribution to the high ceramic dielectric permittivity, instead of the electron-pinned defect-dipoles. PMID:26869187

The formation of nanostructures on rutile (TiO2) surfaces formed after the implantation of kiloelectronvolt-energy Ar_n^+ cluster ions and megaelectronvolt- to gigaelectronvolt-energy multiply charged heavy ions (Iq+, Taq+ and Uq+) is studied. Despite the differences in stopping and energy transfer mechanisms between the kiloelectronvolt-energy cluster ions and megaelectronvolt-energy monoatomic ions, their impacts lead to a similar type of surface damage, namely craters. For the cluster ion implantation the craters are caused by the multiple-collision effect (dominated by nuclear stopping) and the high density of energy and momentum transferred to the target, while for the case of megaelectronvolt multiply charged ions the craters are probably formed due to the Coulomb explosion and fast energy transfer caused by the electronic stopping. At ion energies in the gigaelectronvolt range, nanosize protrusions, so-called hillocks, are observed on the surface. It is suggested that electronic stopping leads to the formation of continuous tracks and the transferred energy is high enough to melt the material along the whole projectile path. Elastic rebound of the tension between the molten and solid state phases leads to liquid flow, expansion and quenching of the melt, thus forming the hillocks. Atomic force microscopy measurements carried out under different environmental conditions (temperature and atmosphere) suggest that the damaged material at the nanosize impact spots has very different water affinity properties (higher hydrophilicity or water adsorption) compared with the non-irradiated rutile surface.

It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting.

We report the acceleration of photoresponsive wettability switching by applying surface fluorination to rutile-TiO2 thin films deposited by reactive sputtering. Photoresponsive wettability switchable surfaces can be applied to optically driven liquid manipulation to enable the elimination of the electrical wiring and pneumatic tubing from fluidic systems. In this work, surface fluorination using CF4 plasma treatment is applied to rutile-TiO2 thin films, which exhibit a wider switching range of wettability than that of anatase-TiO2 thin films. Fluorine termination of TiO2 thin films increases the surface acidity and enhances its photocatalytic performance. TiO2 thin films with and without surface fluorination respectively exhibited the transition of contact angles ranging from 73.7 to 12.3°, and from 70.2 to 32° under UV irradiation for 15 min. Liquid introduction into a microchannel is also demonstrated, utilizing the developed TiO2 surface, which can generate a negative capillary pressure difference under ultraviolet light irradiation.

Titanium dioxide nanoparticles (TiO2NPs), in the two crystalline forms, rutile and anatase, have been widely used in many industrial fields, especially in cosmetics. Therefore, a lot of details about their safety issues have been discussed by the scientific community. Many studies have led to a general agreement about TiO2NPs toxicity, in particular for anatase form, but no mechanism details have been proved yet. In this study, data confirm the different toxic potential of rutile and anatase TiO2NPs in two cell lines up to 5nM nanoparticles concentration. Moreover, we evaluated the role of titanium ions released by TiO2NPs in different conditions, at pH=4.5 (the typical lysosomal compartment pH) and at pH=5.5 (the skin physiological pH) in conditions of darkness and light, to mimic the dermal exposure of cosmetics. Anatase nanoparticles were proner to degradation both in the acidic conditions and at skin pH. Our study demonstrates that pH and sunlight are dominant factors to induce oxidative stress, TiO2NPs degradation and toxicity effects.

The bioactivity of the surface reactive TiO(2) coatings for medical implants can be locally modified by CO(2) laser processing to match with the properties of surrounding tissues. The TiO(2) coatings heat-treated at 500 degrees C exhibit in vitro bioactivity. With further CO(2) laser treatment they exhibit enhanced in vitro bioactivity. The aim of this in vivo study was to compare the performance of heat-treated anatase-structured TiO(2) coatings with preheat-treated and CO(2) laser-treated rutile-structured coatings in terms of their ability to attach soft connective tissues. The coatings were characterized with TF-XRD and AFM. TiO(2)-coated discs were implanted in rats. The samples were analyzed with routine histology, SEM-EDS, and TEM. In both groups, already at 3 days, soft connective tissues were in immediate contact with the surface. No thick crystalline CaP layer was detected by SEM-EDS, but a thin amorphous CaP layer was detected by XPS. No gap between the cell membrane and the coating could be observed in TEM pictures. No differences were observed between the anatase- and rutile-structured coatings in terms of tissue responses. Further studies are needed to verify if the tissues are adherent to the surface of the implant.

Insights into the bonding of As(V) at the metal oxide/aqueous interface can further our understanding of its fate and transport in the environment. The motivation of this work is to explore the interfacial configuration of As(V) on single crystal rutile (110) using grazing-incidence X-ray absorption fine structure spectroscopy (GI-XAFS) and planewave density functional calculations with on-site repulsion (DFT+U). In contrast to the commonly considered corner-sharing bidentate binuclear structure, tetrahedral As(V) binds as an edge/corner-sharing tridentate binuclear complex on rutile (110), as evidenced by observation of three As-Ti distances at 2.83, 3.36, and 4.05 Å. In agreement with the GI-XAFS analysis, our DFT+U calculations for this configuration resulted in the lowest adsorption energy among five possible alternatives. In addition, the electron density difference further demonstrated the transfer of charge between surface Ti atoms and O atoms in AsO4. This charge transfer consequently induced the formation of a chemical bond, which is also confirmed by the partial density of states analysis. Our results may shed new light on coupling the GI-XAFS and DFT approaches to explore molecular-scale adsorption mechanisms on single crystal surfaces.

Modifications induced by 79 MeV Br ions in rutile titanium dioxide thin films, synthesized by dc magnetron sputtering are presented. Irradiations did not induce any new XRD peak corresponding to any other phase. The area and the width of the XRD peaks were considerably affected by irradiation, and peaks shifted to lower angles. But the samples retained their crystallinity at the highest fluence (1 × 1013 ions cm-2) of irradiation even though the electronic energy loss of 79 MeV Br ions far exceeds the reported threshold value for amorphization of rutile TiO2. Fitting of the fluence dependence of the XRD peak area to Poisson equation yielded the radius of ion tracks as 2.4 nm. Ion track radius obtained from the simulation based on the thermal spike model matches closely with that obtained from the fluence dependence of the area under XRD peaks. Williamson-Hall analysis of the XRD spectra indicated broadening and shifting of the peaks are a consequence of irradiation induced defect accumulation leading to microstrains, as was also indicated by Raman and UV-Visible absorption study.

Dielectric spectroscopy is carried out for intrinsic and aluminum-doped TiO2 rutile films which are deposited on RuO2 by the atomic layer deposition technique. Capacitance and conductance are measured in the 0.1 Hz-100 kHz range, for ac electric fields up to 1 MVrms/cm. Intrinsic films have a much lower dielectric constant than rutile crystals. This is ascribed to the presence of oxygen vacancies which depress polarizability. When Al is substituted for Ti, the dielectric constant further decreases. By considering Al-induced modification of polarizability, a theoretical relationship between the dielectric constant and the Al concentration is proposed. Al doping drastically decreases the loss in the very low frequency part of the spectrum. However, Al doping has almost no effect on the loss at high frequencies. The effect of Al doping on loss is discussed through models of hopping transport implying intrinsic oxygen vacancies and Al related centers. When increasing the ac electric field in the MVrms/cm range, strong voltage non-linearities are evidenced in undoped films. The conductance increases exponentially with the ac field and the capacitance displays negative values (inductive behavior). Hopping barrier lowering is proposed to explain high-field effects. Finally, it is shown that Al doping strongly improves the high-field dielectric behavior.

It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting.

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ bindingmore » constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb+ and Na+ reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

The surface phase junction of nanocrystalline TiO2 plays an essential role in governing its photocatalytic activity. Thus, facile and simple methods for preparing phase-junction TiO2 photocatalysts are highly desired. In this work, we show that phase-junction TiO2 is directly synthesized from Ti foil by using a simple calcination method with hydrothermal solution as the precursor below the phase transition temperature. Moreover, the ratio of rutile to anatase in the TiO2 samples could be readily tuned by changing the ratio of weight of Ti foil to HCl, which is used as the hydrothermal precursor, as confirmed by the X-ray diffraction analysis. In the photocatalytic reaction by the TiO2 nanocomposite, a synergistic effect between the two phases within a certain range of the ratio is clearly observed. The results suggest that an appropriate ratio of anatase to rutile in the TiO2 nanocomposite can create more efficient solid-solid interfaces upon calcination, thereby facilitating interparticle charge transfer in the photocatalysis. PMID:26864501

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm-2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm-2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm−2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies. PMID:23286741

Titanium dioxide (TiO2) is an important metal oxide that has been used in many different applications. TiO2 has also been widely employed as a model system to study basic processes and reactions in surface chemistry and heterogeneous catalysis. In this work, we investigated the (011) surface of rutile TiO2 by focusing on its reconstruction. Density functional theory calculations aided by a genetic algorithm based optimization scheme were performed to extensively sample the potential energy surfaces of reconstructed rutile TiO2 structures that obey (2 × 1) periodicity. A lot of stable surface configurations were located, including the global-minimum configuration that was proposed previously. The wide variety of surface structures determined through the calculations performed in this work provide insight into the relationship between the atomic configuration of a surface and its stability. More importantly, several analytical schemes were proposed and tested to gauge the differences and similarities among various surface structures, aiding the construction of the complete pathway for the reconstruction process.

It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O2 on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO2 nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O2 on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O2. Interestingly, this finding is also applicable to the chloride-modified anatase TiO2. This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting. PMID:26906953

Mixed chromium-rhenium oxides, Cr xRe 1-xO 2 with 0.31⩽ x⩽0.66, have been synthesized for the first time by high-pressure high-temperature synthesis and in evacuated quartz tubes. The crystal structures of the compounds have been determined by single crystal and powder X-ray diffraction. Depending on synthesis conditions (pressure and temperature) these phases crystallize either in a tetragonal structure ( P4 2/ mnm) with statistical distribution of metal ions on one site (rutile-type), with cation ordering along c-axis (trirutile-type), or in a monoclinic rutile-like structure ( C2/ m) with ordering of Cr- and Re-cations and metallic Re-Re bonds. The " a" parameter of the tetragonal unit cell increases with increasing Re content whereas the " c" parameter decreases, indicating a strengthening of the Re-Re bond. The thermal stability of tetragonal Cr xRe 1-xO 2 in Ar-atmosphere depends on the Re-content, decomposition is observed at 1241 K for x=0.34, but already at 966 K for x=0.5. The thermal expansion of Cr xRe 1-xO 2 is anisotropic with a larger expansion coefficient in the " c" direction. Tetragonal Cr xRe 1-xO 2 with 0.31⩽ x<0.54 order antiferromagnetically at low temperatures with TN depending on the Cr-content x.

Summary Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV–vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm3+. ICP–AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm3+ was confirmed by X-ray photoelectron spectroscopy and UV–vis spectroscopy: the incorporation of Tm3+ was confirmed by the generation of new absorption bands that could be assigned to Tm3+ transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase. PMID:25821701

Several studies have reported the P- T dependencies of Ti-in-quartz solubility, and there is close agreement among three of the four experimental calibrations. New experiments were conducted in the present study to identify potential experimental disequilibrium, and to determine which Ti-in-quartz solubility calibration is most accurate. Crystals of quartz, rutile and zircon were grown from SiO2-, TiO2-, and ZrSiO4-saturated aqueous fluids in an initial synthesis experiment at 925 °C and 10 kbar in a piston-cylinder apparatus. A range of quartz crystal sizes was produced in this experiment; both large and small examples were analyzed by electron microprobe to determine whether Ti concentrations are correlated with crystal size. Cathodoluminescence images and EPMA measurements show that intercrystalline and intracrystalline variations in Ti concentrations are remarkably small regardless of crystal size. The average Ti-in-quartz concentration from the synthesis experiment is 392 ± 1 ppmw Ti, which is within 95 % confidence interval of data from the 10 kbar isobar of Wark and Watson (Contrib Mineral Petrol 152:743-754, 2006) and Thomas et al. (Contrib Mineral Petrol 160:743-759, 2010). As a cross-check on the Ti-in-quartz calibration, we also measured the concentration of Zr in rutile from the synthesis experiment. The average Zr-in-rutile concentration is 4337 ± 32 ppmw Zr, which is also within the 95 % confidence interval of the Zr-in-rutile solubility calibration of Ferry and Watson (Contrib Mineral Petrol 154:429-437, 2007). The P- T dependencies of Ti solubility in quartz and Zr solubility in rutile were applied as a thermobarometer to the experimental sample. The average Ti-in-quartz isopleth calculated from the calibration of Thomas et al. (Contrib Mineral Petrol 160:743-759, 2010) and the average Zr-in-rutile isopleth calculated from the calibration of Tomkins et al. (J Metamorph Geol 25:703-713, 2007) cross at 9.5 kbar and 920 °C, which is in excellent

Epitaxial rutile-structured single-crystal MnxTi1 - xO2 - δ films were synthesized on rutile- (110) and -(001) substrates using pulsed laser deposition. The films were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and aberration-corrected transmission electron microscopy (ACTEM). Under the present conditions, 400 °C and PO2 = 20 mTorr, single crystal epitaxial thin films were grown for x = 0.13, where x is the nominal average mole fraction of Mn. In fact, arbitrarily thick films could be grown with near invariant Mn/Ti concentration profiles from the substrate/film interface to the film surface. In contrast, at x = 0.25, Mn became enriched towards the surface and a secondary nano-scale phase formed which appeared to maintain the basic rutile structure but with enhanced z-contrast in the tunnels, or interstitial sites. Ab initio thermodynamic calculations provided quantitative estimates for the destabilizing effect of expanding the β-MnO2 lattice parameters to those of TiO2-rutile, the stabilizing effect of diluting Mn with increasing Ti concentration, and competing reaction pathways for surface oxide formation.

Epitaxial rutile-structured single-crystal MnxTi1-xO2-δ films were synthesized on rutile- (110) and -(001) substrates using pulsed laser deposition. The films were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and aberration-corrected transmission electron microscopy (ACTEM). Under the present conditions, 400oC and PO2 = 20 mTorr, single crystal epitaxial thin films were grown for x = 0.13, where x is the nominal average mole fraction of Mn. In fact, arbitrarily thick films could be grown with near invariant Mn/Ti concentration profiles from the substrate/film interface to the film surface. In contrast, at x = 0.25, Mn became enriched towards the surface and a secondary nano-scale phase formed which appeared to maintain the basic rutile structure but with enhanced z-contrast in the tunnels, or tetrahedral interstitial sites. Ab initio thermodynamic calculations provided quantitative estimates for the destabilizing effect of expanding the β-MnO2 lattice parameters to those of TiO2-rutile, the stabilizing effect of diluting Mn with increasing Ti concentration, and competing reaction pathways.

Time-resolved vibrational sum frequency generation (VSFG) spectroscopy has been used to investigate the vibrational relaxation dynamics of the rhenium bipyridyl CO2-reduction catalyst Re(CO)3Cl(dcbpy) [dcbpy = 4,4‧-dicarboxy-2,2‧-bipyridine] adsorbed onto the (1 1 0) surface of a Rutile TiO2 single crystal. IR pump-VSFG probe spectra of the a‧(1) CO stretching mode indicate a ultrafast population equilibration between three CO stretching modes followed by their population relaxation via intramolecular vibrational energy transfer. Similar vibational relaxation dynamics was also observed for the same complex on anatase TiO2 nanocrystalline thin films measured by IR pump-IR probe transient absorption spectroscopy. The relaxation dynamics of ReCOA on TiO2, in DMF solution, and immobilized on Au through alkane thiol linkers were compared to examine possible effects of adsorbate-TiO2 interaction.

An effective non-metal (N) and non-transition metal (Sb) passivated co-doping approach is proposed to improve the photoelectochemical performance of rutile TiO{sub 2} for water-splitting by using first-principles calculations. It is found that the band edges of N + Sb co-doped TiO{sub 2} match with the redox potentials of water, and a narrow band gap (2.0 eV) is achieved for enhanced visible light absorption. The compensated donor (Sb) and acceptor (N) pairs could prevent the recombination of photo-generated electron-hole pairs. In addition, the N + Sb defect pairs tend to bind with each other, which could enhance the stability and N concentration of the system.

The density functional theory is used to examine the electronic structure of small Au clusters, supported on rutile TiO(2)(110) surfaces having subsurface Ti-interstitials. The interstitials reduce the surface and we find that negatively charged gold clusters are stabilized with respect to the stoichiometric surface. The behavior of the open-shell gold clusters can be rationalized in terms of the highest occupied molecular orbitals and the resulting electron affinities. The relative stabilities of closed-shell gold clusters led to recent disagreements in the literature. We show that they are very dependent on the density functional used. As expected, a redshift in the CO stretch vibration is calculated for CO adsorbed on a negatively charged cluster. Somewhat surprisingly a larger redshift is found for CO adsorbed on an overall positively charged Au(3) cluster. This is explained by CO being a local probe of the individual Au charges and one Au atom having an electron accumulation.

Zinc-protoporphyrin, adsorbed on the rutile TiO{sub 2}(110) surface, has been studied using photoemission spectroscopy and near-edge absorption fine structure spectroscopy to deduce the nature of the molecule-surface bonding and the chemical environment of the central metal atom. To overcome the difficulties associated with sublimation of the porphyrin molecules, samples were prepared in situ using ultrahigh vacuum electrospray deposition, a technique which facilitates the deposition of nonvolatile and fragile molecules. Monolayers of Zn protoporphyrin are found to bond to the surface via the oxygen atoms of the deprotonated carboxyl groups. The molecules initially lie largely parallel to the surface, reorienting to an upright geometry as the coverage is increased up to a monolayer. For those molecules directly chemisorbed to the surface, the interaction is sufficiently strong to pull the central metal atom out of the molecule.

Titanium dioxide phases are important due to their special potential for use in a broad range of applications particularly low-cost solar cells. However, this potential is actually restricted by the wide band gaps of TiO2 phases. A way to overcome this limitation is to reduce the band gap by incorporating nonmetal dopants into TiO2. For this purpose, in this paper, the effect of F and N doping on different sizes of rutile TiO2 quantum dots (QDs) was investigated using density functional theory (DFT) calculations. The results indicated that unlike nitrogen, doping of fluorine increases the efficiency of the quantum dot solar cells as a consequence of reducing auger recombination. Moreover, it was observed that when the size of QDs increases, shifting of the Fermi level towards the conduction band occurs as a favorable effect for solar cells.

The adsorption of malonic acid on rutile TiO2 (110) has been studied using photoelectron spectroscopy and C K-edge, near edge X-ray fine structure spectroscopy (NEXAFS). Analysis of the O 1s and Ti 2p spectra suggest that the molecule adsorbs dissociatively in a doubly-bidentate adsorption geometry as malonate. The data are unable to distinguish between a chelating bonding mode with the backbone of the molecule lying along the [001] azimuth or a bridging geometry along the direction. Work carried out on a wiggler beamline suggests that the molecule is unstable under irradiation by high-flux synchrotron radiation from this type of insertion device.

Softening and stiffening of phonons in rutile titanium dioxide films are investigated by in situ micro-Raman studies during energetic ion irradiation. The in situ study minimized other possible mechanisms of phonon dynamics. Initial softening and broadening of Raman shift are attributed to the phonon confinement by structural defects and loss of stoichiometry. The stiffening of A{sub 1g} mode is ascribed to large distortion of TiO{sub 6} octahedra under the influence of lattice strain in the (110) plane, which gives rise to lengthening of equatorial Ti-O bond and shortening of apical Ti-O bond. The shortening of apical Ti-O bond induces stiffening of A{sub 1g} mode in the framework of the bond-order-length-strength correlation mechanism.

Immobilization of nanoparticles on inorganic supports has been recently developed, resulting in the creation of nanocomposites. Concerning titanium dioxide nanoparticles (TiO2 NPs(1)), these have already been developed in conjugation with clays, but so far there are no available toxicological studies on these nanocomposites. The present work intended to evaluate the hepatic toxicity of nanocomposites (C-TiO2(2)), constituted by rutile TiO2 NPs immobilized in nanokaolin (NK(3)) clay, and its individual components. These nanomaterials were analysed by means of FE-SEM(4) and DLS(5) analysis for physicochemical characterization. HepG2 cells were exposed to rutile TiO2 NPs, NK clay and C-TiO2 nanocomposite, in the presence and absence of serum for different exposure periods. Possible interferences with the methodological procedures were determined for MTT,(6) neutral red uptake, alamar blue (AB), LDH,(7) and comet assays, for all studied nanomaterials. Results showed that MTT, AB and alkaline comet assay were suitable for toxicity analysis of the present materials after slight modifications to the protocol. Significant decreases in cell viability were observed after exposure to all studied nanomaterials. Furthermore, an increase in HepG2 DNA damage was observed after shorter periods of exposure in the absence of serum proteins and longer periods of exposure in their presence. Although the immobilization of nanoparticles in micron-sized supports could, in theory, decrease the toxicity of single nanoparticles, the selection of a suitable support is essential. The present results suggest that NK clay is not the appropriate substrate to decrease TiO2 NPs toxicity. Therefore, for future studies, it is critical to select a more appropriate substrate for the immobilization of TiO2 NPs.

Knowledge of the alignment of molecular frontier levels in the ground state can be used to predict the photocatalytic activity of an interface. The position of the adsorbate’s highest occupied molecular orbital (HOMO) levels relative to the substrate’s valence band maximum (VBM) in the interface describes the favorability of photogenerated hole transfer from the VBM to the adsorbed molecule. This is a key quantity for assessing and comparing H2O photooxidation activities on two prototypical photocatalytic TiO2 surfaces: anatase (A)-TiO2(101) and rutile (R)-TiO2(110). Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) G0W0 calculations, we assess the relative photocatalytic activity of intact and dissociated H2O on coordinately unsaturated (Ticus) sites of idealized stoichiometric A-TiO2(101)/R-TiO2(110) and bridging O vacancies (Obrvac) of defective A-TiO2-x(101)/R-TiO2-x(110) surfaces (x = 1/4, 1/8) for various coverages. Such a many-body treatment is necessary to correctly describe the anisotropic screening of electron-electron interactions at a photocatalytic interface and, hence, obtain accurate interfacial level alignments. The more favorable ground state HOMO level alignment for A-TiO2(101) may explain why the anatase polymorph shows higher photocatalytic activities than the rutile polymorph. Our results indicate that (1) hole trapping is more favored on A-TiO2(101) than RTiO2(110) and (2) HO@Ticus is more photocatalytically active than intact H2O@Ticus.

To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti0.99Co0.01O2 and ferromagnetic Ti0.95Co0.05O2 films. The Co atoms in the Ti0.99Co0.01O2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO2Ti4 formed around Co in the Ti0.95Co0.05O2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. As a result, the suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO2.

Although the rutile structure of TiO2 is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000 K. In this paper, inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO2 from 300 to 1373 K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of 3d electrons of Ti and 2p electrons of O atoms. Finally, with thermal expansion, the energy variation in this “phonon-tracked hybridization” flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.

Different polymorphs of MRe 2O 6 ( Mdbnd Fe, Co, Ni) with rutile-like structures were prepared using high-pressure high-temperature synthesis. For syntheses temperatures higher than ˜1573 K, tetragonal rutile-type structures ( P4 2/ mnm) with a statistical distribution of M- and Re-atoms on the metal position in the structure were observed for all three compounds, whereas rutile-like structures with orthorhombic or monoclinic symmetry, partially ordered M- and Re-ions on different sites and metallic Re-Re-bonds within Re 2O 10-pairs were found for CoRe 2O 6 and NiRe 2O 6 at a synthesis temperature of 1473 K. According to the XPS measurements, a mixture of Re +4/Re +6 and M2+/ M3+ is present in both structural modifications of CoRe 2O 6 and NiRe 2O 6. The low-temperature forms contain more Re +4 and M 3+ than the high-temperature forms. Tetragonal and monoclinic modifications of NiRe 2O 6 order with a ferromagnetic component at ˜24 K, whereas tetragonal and orthorhombic CoRe 2O 6 show two magnetic transitions: below ˜17.5 and 27 K for the tetragonal and below 18 and 67 K for the orthorhombic phase. Tetragonal FeRe 2O 6 is antiferromagnetic below 123 K.

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (110), (010), (101) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximately = (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

We describe properties of MIM capacitor structures with the RuO2 bottom electrode, TiO2 dielectric film and various top electrodes. The TiO2 films were grown by atomic layer deposition (ALD) at temperature 425 °C on metal organic chemical vapour deposited (MOCVD) RuO2 bottom electrodes grown at 300 °C. Due to local epitaxial growth on the RuO2 rutile structure, TiO2 films with the permittivity 135 and equivalent oxide thickness 0.58 nm were obtained. Capacitance density as high as 60 fF/μm2 was achieved. Au and Ni films for top electrodes were prepared by evaporation at room temperature. RuO2 films for top electrodes were grown by MOCVD. Strong effect of top electrode material on capacitance and leakage currents was observed. In addition, the stacks with TiO2 dielectric were found to be very sensitive to oxygen post-deposition treatment.

Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)

Hierarchically assembled flower-like rutile TiO2 (FLH-R-TiO2) nanostructures were successfully synthesized from TiCl4 at room temperature without the use of surfactants or templates. An initial sol-gel synthesis at room temperature allowed long-term hydrolysis and condensation of the precursors. The resulting FLH-R-TiO2 possessed relatively high crystallinity (85 wt%) and consisted of rod-shaped subunits assembling into cauliflower-like nanostructures. Hydrothermal evolution of FLH-R-TiO2 at different temperatures (150, 200 and 250 °C) was followed by means of X-ray diffraction, transmission and scanning electron microscopy. These FLH-R-TiO2 nanostructures were tested as photocatalysts under simulated daylight (full-spectrum lighting) in the degradation of methyl orange and in the inactivation of a multiresistant bacterium, Klebsiella pneumoniae. The effects of hydrothermal treatment on the structure, photocatalytic behavior and antibacterial activity of FLH-R-TiO2 are discussed.

A fully atomistic model of a compact electric double layer at the rutile TiO2(1 1 0)-water interface is constructed by adding protons to bridging oxygens or removing them from H2O molecules adsorbed on terminal metal cation sites. The surface charge is compensated by F(-) or Na(+) counter ions in outer as well as inner sphere coordination. For each of the protonation states the energy of the TiO2 conduction band minimum is determined relative to the standard hydrogen electrode by computing the free energy for the combined insertion of an electron in the solid and a proton in solution away from the double layer using density functional theory based molecular dynamics methods. Interpreted as electrode potentials, this gives an estimate of the capacitance which is compared to the capacitance obtained from the difference in the average electrostatic potentials in the solid and aqueous phase. When aligned at the point of zero charge these two methods lead to almost identical potential-charge profiles. We find that inner sphere complexes have a slightly larger capacitance (0.4 F m(-2)) compared to outer sphere complexes (0.3 F m(-2)).

Periodic hybrid-exchange density functional theory calculations are used to predict the structure of water on the rutile TiO2(110) surface (Θ⩽ 1 ML), which is an important first step towards understanding the photocatalytic processes that occur in solar water splitting. A detailed model describing the water-water and water-surface interactions is developed by exploring thoroughly the adsorption energetics. The possible adsorption mode—molecular, dissociative, or mixed—and the binding energy are studied as a function of coverage and arrangement, thus separation, of adsorbed species. These dependencies (coverage and arrangement) have a significant influence on the nature of the interactions involved in the H2O-TiO2 system. The importance of both direct intermolecular and surface-mediated interactions between surface species is emphasized. Finally, to gain insight into the photooxidation of adsorbed species at the surface, the electronic structure of the predicted adsorbate-substrate geometries is analyzed in terms of total and projected density of states.

Herein, we report a photocatalytic heterojunction device of rutile TiO2 nanorod arrays based on a p-n silicon junction (TiO2@PN) and its full absorption of ultraviolet and visible light for synergistic photodegradation. The fabricated TiO2@PN had excellent photocatalytic degradation of methyl orange (MO) under irradiation of a 300 W Xe lamp, and its pseudo-first-order rate constant k was 0.221 h(-1), which was greatly higher than that for TiO2 nanorod arrays based on an n-p silicon junction (TiO2@NP, 0.078 h(-1)) and glass (TiO2@G, 0.032 h(-1)). The higher photocatalytic performance of TiO2@PN could be attributed to the fact that the photovoltage (PV) of the p-n junction promotes separation of the electron-hole pairs of the TiO2, and the holes are thus left within the TiO2 nanorods to produce a strong oxidant of hydroxyl radicals (˙OH). Moreover, this heterojunction device could be easily fabricated in a large size for easy recovery and recycling, which shows its promise in the solar-driven degradation of environmental pollution.

Well-aligned densely-packed rutile TiO2 nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC3H7)4) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ~33° from the normal to substrates. TEM and SAED measurements showed that the TiO2 NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO2 NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO2 NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

This paper reveals the fact that the O adatoms (Oad) adsorbed on the 5-fold Ti rows of rutile TiO2(110) react with CO to form CO2 at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO2(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ˜1.5 nm and two-atomic layer height corresponding to ˜50 Au atoms/cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO2(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O2 adsorption on the surface and also enhance the reaction of CO with the Oad atoms to form CO2 owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

Epitaxial SrTiO{sub 3} films were fabricated by laser molecular beam epitaxy on bare and TiO{sub 2} buffered GaN(0002), respectively. The whole deposition processes were in situ monitored by reflection high energy electron diffraction (RHEED). X-ray diffraction (XRD) was carried out to study the growth orientation and crystalline quality of STO films. The interfacial characters and epitaxial relationships were also investigated by high revolution transition electron microscope and selected area electron diffraction (SAED). According to the RHEED observation, the lowest epitaxy temperature of STO on TiO{sub 2} buffered GaN was decreased compared with the direct deposited one. The epitaxial relationship was (111)[110]STO//(0002)[1120]GaN in both cases as confirmed by RHEED, XRD, and SAED. The full width at half maximum of omega-scan and PHI-scan of STO on TiO{sub 2} buffered GaN was reduced compared with that deposited on bare GaN, indicating that epitaxial quality of STO film is improved by inserting TiO{sub 2} layer. In summary, the lattice mismatch was reduced by inserting rutile TiO{sub 2}. As a result, the crystalline temperature was reduced and enhanced epitaxial quality of STO thin film was obtained.

TiO{sub 2} is a wide band gap semiconductor with important applications in photovoltaic cells and photocatalysis. In this paper, we report synthesis of single-crystalline rutile phase TiO{sub 2} nanowires on arbitrary substrates, including fluorine-doped tin oxide (FTO), glass slides, tin-doped indium oxide (ITO), Si/SiO{sub 2}, Si(100), Si(111), and glass rods. By controlling the growth parameters such as growth temperature, precursor concentrations, and so forth, we demonstrate that anisotropic growth of TiO{sub 2} is possible leading to various morphologies of nanowires. Optimization of the growth recipe leads to well-aligned vertical array of TiO{sub 2} nanowires on both FTO and glass substrates. Effects of various titanium precursors on the growth kinetics, especially on the growth rate of nanowires, are also studied. Finally, application of vertical array of TiO{sub 2} nanowires on FTO as the photoanode is demonstrated in dye-sensitized solar cell with an efficiency of 2.9 ± 0.2%.

This paper reveals the fact that the O adatoms (O{sub ad}) adsorbed on the 5-fold Ti rows of rutile TiO{sub 2}(110) react with CO to form CO{sub 2} at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO{sub 2}(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of {approx}1.5 nm and two-atomic layer height corresponding to {approx}50 Au atoms/cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO{sub 2}(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O{sub 2} adsorption on the surface and also enhance the reaction of CO with the O{sub ad} atoms to form CO{sub 2} owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ∼1.5 nm and two-atomic layer height corresponding to ∼50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.

Experimental philosophy is a new interdisciplinary field that uses methods normally associated with psychology to investigate questions normally associated with philosophy. The present review focuses on research in experimental philosophy on four central questions. First, why is it that people's moral judgments appear to influence their intuitions about seemingly nonmoral questions? Second, do people think that moral questions have objective answers, or do they see morality as fundamentally relative? Third, do people believe in free will, and do they see free will as compatible with determinism? Fourth, how do people determine whether an entity is conscious?

The cation in the electrolyte of the dye-sensitized solar cell (DSSC) has a profound effect on electron trapping and transport behavior in TiO2 nanocrystalline film; this is one of the important factors that determines the overall efficiency of DSSCs. Here, we present a quantum mechanical investigation on the structures and energetics of proton-induced electron trap states and the thermodynamical barrier heights for the ambipolar diffusion of proton/electron pair using a large cluster model for the computations. Our calculations indicate that protons react with TiO2 to form covalent O-H bonds. This is in contrast to the reaction of Li(+) with TiO2, in which case the alkali metal is more accurately described as a simple coordinating cation. The covalent O-H bonding leads both to deeper electron trap states and to significantly higher barriers for the diffusion of carriers. These results are qualitatively consistent with experimental observations, and they extend our understanding of the cation effect in DSSCs at an atomic level of detail.

The specific chemical composition of monazite in shear zones is controlled by the syndeformation dissolution-precipitation reactions of the rock-forming minerals. This relation can be used for dating deformation, even when microfabric characteristics like shape preferred orientation or intracrystalline deformation of monazite itself are missing. Monazite contemporaneously formed in and around the shear zones may have different compositions. These depend on the local chemical context rather than reflecting successive crystallization episodes of monazite. This is demonstrated in polymetamorphic, mylonitic high-pressure (HP) garnet-kyanite granulites of the Alpine Sidironero Complex (Rhodope UHP terrain, Northern Greece). The studied mylonitic rocks escaped from regional migmatization at 40-36 Ma and from subsequent shearing through cooling until 36 Ma. In-situ laser-ablation split-stream inductively-coupled plasma mass spectrometry (LASS) analyses have been carried out on monazite from micro-scale shear zones, from pre-mylonitic microlithons as well as of monazite inclusions in relictic minerals complimented by U-Pb data on rutile and Rb-Sr data of biotite. Two major metamorphic episodes, Mesozoic and Cenozoic, are constrained. Chemical compositions, isotopic characteristics and apparent ages systematically vary among monazite of four different microfabric domains (I-IV). Within three pre-mylonitic domains (inclusions in (I) pre-mylonitic kyanite and (II) garnet porphyroclasts, and (III) in pre-mylonitic microlithons) monazite yields ages of ca. 130-150 Ma for HP-granulite metamorphism, in line with previous geochronological results in the area. Patchy alteration of the pre-mylonitic monazite by intra-grain dissolution-precipitation processes variably increased negative Eu anomaly and reduced the HREE contents. The apparent age of this altered monazite is reduced. Monazite in the syn-mylonitic shear bands (IV) differs in chemical composition from unaltered and

Understanding agglomeration of late transition metal atoms, such as Pd, on metal oxide supports, such as TiO2, is critical for designing heterogeneous catalysts as well as for controlling metal/oxide interfaces in general. One approach for reducing particle sintering is to modify the metal oxide surface with hydroxyls that decrease adatom mobility. We study by scanning tunneling microscopy experiments, density functional theory (DFT) calculations, and Monte Carlo (MC) computer simulations the atomistic processes of Pd sintering on a hydroxyl-modified TiO2(011)-2 × 1 surface. The formation of small 1-3 atom clusters that are stable at room temperature is achieved on the hydroxylated surface, while much larger clusters are formed under the same conditions on a hydroxyl-free surface. DFT shows that this is a consequence of stronger binding of Pd atoms adjacent to hydroxyls and increased surface diffusion barriers for Pd atoms on the hydroxylated surface. DFT, kinetic MC, and ReaxFF-based NVT-MC simulations show that Pd clusters larger than single Pd monomers can adsorb the hydrogen from the oxide surface and form Pd hydrides. This depletes the surface hydroxyl coverage, thus allowing Pd to more freely diffuse and agglomerate at room temperature. Experimentally, this causes a bimodal cluster size distribution with 1-3 atom clusters prevalent at low Pd coverage, while significantly larger clusters become dominant at higher Pd concentrations. This study demonstrates that hydroxylated oxide surfaces can significantly reduce Pd cluster sizes, thus enabling the preparation of surfaces populated with metal clusters composed of single to few atoms.

In this report, local electronic structures of steps and terraces on rutile TiO{sub 2} single crystal faces were studied by second harmonic and sum frequency generation (SHG/SFG) spectroscopy. We attained selective measurement of the local electronic states of the step bunches formed on the vicinal (17 18 1) and (15 13 0) surfaces using a recently developed step-selective probing technique. The electronic structures of the flat (110)-(1x1) (the terrace face of the vicinal surfaces) and (011)-(2x1) surfaces were also discussed. The SHG/SFG spectra showed that step structures are mainly responsible for the formation of trap states, since significant resonances from the trap states were observed only from the vicinal surfaces. We detected deep hole trap (DHT) states and shallow electron trap (SET) states selectively from the step bunches on the vicinal surfaces. Detailed analysis of the SHG/SFG spectra showed that the DHT and SET states are more likely to be induced at the top edges of the step bunches than on their hillsides. Unlike the SET states, the DHT states were observed only at the step bunches parallel to [1 1 1][equivalent to the step bunches formed on the (17 18 1) surface]. Photocatalytic activity for each TiO{sub 2} sample was also measured through methylene blue photodegradation reactions and was found to follow the sequence: (110) < (17 18 1) < (15 13 0) < (011), indicating that steps along [0 0 1] are more reactive than steps along [1 1 1]. This result implies that the presence of the DHT states observed from the step bunches parallel to [1 1 1] did not effectively contribute to the methylene blue photodegradation reactions.

In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO2(110) to form N2O, which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a by-product of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

Regenerated cellulose membrane was used as bio-template nanoreactor for the formation of rutile TiO2 mesoporous, as well as in-situ carbon dopant in acidified sol-gel system. The effects of calcination temperature on the physicochemical characteristic of core-shell nanostructured of bio-templated C-doped mesoporous TiO2 are highlighted in this study. By varying the calcination temperature, the thickness of the carbon shell coating on TiO2, crystallinity, surface area, and optical properties could be tuned as confirmed by HRTEM, nitrogen adsorption/desorption measurement, XRD and UV-vis-NIR spectroscopy. The results suggested that increment in the calcination temperature would lead to the band gap narrowing from 2.95 to 2.80 eV and the thickness of carbon shell increased from 0.40 to 1.20 nm. The x-ray photoelectron spectroscopy showed that the visible light absorption capability was mainly due to the incorporation of carbon dopant at interstitial position in the TiO2 to form Osbnd Tisbnd C or Tisbnd Osbnd C bond. In addition, the formation of the carbon core-shell nanostructured was due to carbonaceous layer grafted onto the surface of TiO2 via Tisbnd Osbnd C and Tisbnd OCO bonds. The result indicated that bio-templated C-doped core-shell mesoporous TiO2 prepared at 300 °C exhibited the highest photocatalytic activity. It is worthy to note that, the calcination temperature provided a huge impact towards improving the physicochemical and photocatalytic properties of the prepared bio-templated C-doped core-shell mesoporous TiO2.

A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions and approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.

The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm-1 are observed for stretching vibrations of ODb and OHb on TiO2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O2 or annealed in the temperature range of 400 – 600 K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with Ea = 0.545 eV, ΔEa(FWHM) = 0.125 eV, and a “normal” prefactor, v = 1012 s-1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti5c rows on the reduced TiO2

Millions of animals are used every year in often times extremely painful and distressing scientific procedures. Legislation of animal experimentation in modern societies is based on the supposition that this is ethically acceptable when certain more or less defined formal (e.g. logistical, technical) demands and ethical principles are met. The main parameters in this context correspond to the "3Rs" concept as defined by Russel and Burch in 1959, i.e. that all efforts to replace, reduce and refine experiments must be undertaken. The licensing of animal experiments normally requires an ethical evaluation process, often times undertaken by ethics committees. The serious problems in putting this idea into practice include inter alia unclear conditions and standards for ethical decisions, insufficient management of experiments undertaken for specific (e.g. regulatory) purposes, and conflicts of interest of ethics committees' members. There is an ongoing societal debate about ethical issues of animal use in science. Existing EU legislation on animal experimentation for cosmetics testing is an example of both the public will for setting clear limits to animal experiments and the need to further critically examine other fields and aspects of animal experimentation.

Impurity doping is a simple and efficient modification method to improve the photocatalytic performance of wide band gap photocatalysts. However, some basic and important issues about the mechanism of impurity doping modification still need to be further confirmed and explained. In the present work, Pr-doped TiO2 with a mono-phase crystal structure was prepared by a sol-gel method. Then, the crystal structure, binding information, optical absorption, and photocatalytic activity were systematically investigated. The experimental results show that Pr doping could significantly enhance the photocatalytic activity of TiO2, and the effects of modification on rutile TiO2 are more obvious than for anatase TiO2. In order to understand the underlying mechanism, density functional theory was utilized to calculate the crystal structure and electronic structure of pure and Pr-doped TiO2. The differences in electronic structure between anatase and rutile phases lead to the above photocatalytic performance. The experimental measurements and theoretical calculations mutually support each other in the present work. Two points are confirmed: the position of the band edge determines the redox activity of the photocatalyst, and the shallow energy bands induced by impurity doping could improve the photocatalytic performance.

Calibration materials for microanalysis of Ti minerals have been prepared by direct fusion of synthetic and natural materials by resistance heating in high-purity graphite electrodes. Synthetic materials were FeTiO3 and TiO2 reagents doped with minor and trace elements; CRMs for ilmenite, rutile, and a Ti-rich magnetite were used as natural materials. Problems occurred during fusion of Fe2O3-rich materials, because at atmospheric pressure Fe2O3 decomposes into Fe3O4 and O2 at 1462 degrees C. An alternative fusion technique under pressure was tested, but the resulting materials were characterized by extensive segregation and development of separate phases. Fe2O3-rich materials were therefore fused below this temperature, resulting in a form of sintering, without conversion of the materials into amorphous glasses. The fused materials were studied by optical microscopy and EPMA, and tested as calibration materials by inductively coupled plasma mass spectrometry, equipped with laser ablation for sample introduction (LA-ICP-MS). It was demonstrated that calibration curves based on materials of rutile composition, within normal analytical uncertainty, generally coincide with calibration curves based on materials of ilmenite composition. It is, therefore, concluded that LA-ICP-MS analysis of Ti minerals can with advantage be based exclusively on calibration materials prepared for rutile, thereby avoiding the special fusion problems related to oxide mixtures of ilmenite composition. It is documented that sintered materials were in good overall agreement with homogeneous glass materials, an observation that indicates that in other situations also sintered mineral concentrates might be a useful alternative for instrument calibration, e.g. as alternative to pressed powders.

The convergence of several disparate research programmes raises the possibility that the long-term evolutionary processes of innovation and radiation may become amenable to laboratory experimentation. Ancestors might be resurrected directly from naturally stored propagules or tissues, or indirectly from the expression of ancestral genes in contemporary genomes. New kinds of organisms might be evolved through artificial selection of major developmental genes. Adaptive radiation can be studied by mimicking major ecological transitions in the laboratory. All of these possibilities are subject to severe quantitative and qualitative limitations. In some cases, however, laboratory experiments may be capable of illuminating the processes responsible for the evolution of new kinds of organisms. PMID:26763705

The spinel Li4Ti5O12/rutile-TiO2@carbon (LTO-RTO@C) composites were fabricated via a hydrothermal method combined with calcination treatment employing glucose as carbon source. The carbon coating layer and the in situ formed rutile-TiO2 can effectively enhance the electric conductivity and provide quick Li(+) diffusion pathways for Li4Ti5O12. When used as an anode material for lithium-ion batteries, the rate capability and cycling stability of LTO-RTO@C composites were improved in comparison with those of pure Li4Ti5O12 or Li4Ti5O12/rutile-TiO2. Moreover, the potential of approximately 1.8 V rechargeable full lithium-ion batteries has been achieved by utilizing an LTO-RTO@C anode and a LiFePO4@N-doped carbon cathode.

This study aims to enhance the mechanical properties, thermal stability, weathering resistance and antibacterial property of a styrene acrylic polyurethane coating by adding rutile titania dioxide (R-TiO2) nanoparticles in coating formulation. The styrene acrylic polyurethane/R-TiO2 nanocomposite had been prepared by using ultrasonication. The effects of nanoparticles on the mechanical properties, thermal stability and weathering resistance of as-prepared coatings were investigated by using the adhesion strength and ball impact tests, the Fourier transform infrared and UV-vis analyses, thermogravimetric analysis (TGA), and UV/condensation weathering chamber equipped with UVA-340 fluorescent lamps, respectively. The disperse quality of nanoparticles in the coating was examined by using the field emission scanning electron microscope (FESEM). The mechanical test results showed that suitable content of R-TiO2 nanoparticles in the nanocomposite coating was 2 wt%. The FESEM images indicated that the nanoparticles were dispersed homogeneously into the entire volume of the coating. For the nanocomposite prepared by 3 h of ultrasonication, the average size of nanoparticles was in range of 40-50 nm. The ball impact and adhesion tests showed that the incorporation of nanoparticles into the coating significantly enhanced the impact strength from 120 to 145 kg cm and increased the adhesion from level 1 to level 0. The TGA test illustrated that in presence of nanoparticles, the decomposition temperature of coating increased from 146.9 °C to 154.21 °C. For the temperature at 50% loss in mass (T 50%), it was found that the T 50% of the neat coating is 351.86 °C. Adding the 2 wt% R-TiO2 nanoparticles into coating increased the T 50% value to 360.06 °C. After UV/condensation accelerated weathering test (30 cycles), the significant improvement in weight loss, impact strength and adhesion of the neat coating was observed with the presence of nanoparticles. The antibacterial test

Nb and In co-doped rutile TiO2 nanoceramics (n-NITO) were successfully synthesized through a chemical-solution route combined with a low temperature spark plasma sintering (SPS) technique. The particle morphology and the microstructure of n-NITO compounds were nanometric in size. Various techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG)/differential thermal analysis (DTA), Fourier transform infrared (FTIR), and Raman spectroscopy were used for the structural and compositional characterization of the synthesized compound. The results indicated that the as-synthesized n-NITO oxalate as well as sintered ceramic have a co-doped single phase of titanyl oxalate and rutile TiO2, respectively. Broadband impedance spectroscopy revealed that novel colossal permittivity (CP) was achieved in n-NITO ceramics exhibiting excellent temperature-frequency stable CP (up to 10(4)) as well as low dielectric loss (∼5%). Most importantly, detailed impedance data analyses of n-NITO compared to microcrystalline NITO (μ-NITO) demonstrated that the origin of CP in NITO bulk nanoceramics might be related with the pinned electrons in defect clusters and not to extrinsic interfacial effects.

We report a highly efficient solar cell based on a submicrometer (~0.6 μm) rutile TiO2 nanorod sensitized with CH3NH3PbI3 perovskite nanodots. Rutile nanorods were grown hydrothermally and their lengths were varied through the control of the reaction time. Infiltration of spiro-MeOTAD hole transport material into the perovskite-sensitized nanorod films demonstrated photocurrent density of 15.6 mA/cm(2), voltage of 955 mV, and fill factor of 0.63, leading to a power conversion efficiency (PCE) of 9.4% under the simulated AM 1.5G one sun illumination. Photovoltaic performance was significantly dependent on the length of the nanorods, where both photocurrent and voltage decreased with increasing nanorod lengths. A continuous drop of voltage with increasing nanorod length correlated with charge generation efficiency rather than recombination kinetics with impedance spectroscopic characterization displaying similar recombination regardless of the nanorod length.

Photoemission is a well-known mechanism for release of electrons from a surface during electrical breakdown of a gas such as air. During air breakdown, UV photons, which are emitted from the highly excited gas molecules, are absorbed in the surfaces such as the cathode and the anode. These absorbed photons create energetic electrons, and a small portion of these electrons reach the surface. Those that overcome the potential energy barrier at the surface tend to be emitted. In this talk, the Boltzmann equation that describes these phenomena is formulated. A Monte Carlo probabilistic method is used to obtain the rate of electron emission as a function of photon energy. The role of bandstructure effects will be discussed. This bandstructure information is obtained by using a density-functional theory (DFT) method. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Al/TiO2/p-Si and Al/TİO2/Al2O3/p-Si samples were prepared using the atomic layer deposition method (ALD) and their gas sensing properties were investigated. The electrical properties of the samples were studied using a two probe method in the temperature range 25-230 °C and at room temperature UV conditions. The TiO2/Al2O3 heterojunction sample exhibited an excellent gas sensing response to CO2 gas at room temperature and improved the effect of UV light irradiation. The results showed that heterostructures helped to improve the gas sensor properties, affected the sensing at room temperature and thus guided the design of photocatalysts. The TiO2/Al2O3 heterojunction prepared using this method can be used as a material for semiconductor gas sensors detecting poisonous gases like CO2 at room temperature with high sensitivity and selectivity.

We study the color fading of paints films composed of mixtures of white rutile titanium dioxide and yellow arylide pigments dispersed in two polymer binders at different volume concentrations. The samples were exposed to ultraviolet radiations in an accelerated weathering tester during three weeks. The measured patterns in color variations appeared to be independent of the chemistry of the binders. We then developed a theoretical framework, based on the Radiative transfer Equation of light and the One Particle T-Matrix formalism to simulate the color fading process. The loss of color is correlated to the progressive decrease of the original colored pigment volume-filling fraction as the destructive UV radiations penetrate deeper into the films. The calculated patterns of color variations of paints film composed by mixtures of white pigments with yellow Cadmium Sulfate (CdS) and red Cerium Sulfide (Ce2S3) pigments showed the same trend as that seen experimentally.

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb+ and Na+ reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.

We have used spin-polarized density functional theory (DFT) to study O(2) evolution on a clean partially reduced rutile TiO(2)(110) surface (i.e., a surface having oxygen vacancies) and its interaction with Au(1) or Au(2) cluster adsorbed on it. We assume that the total spin of the electronic wave function is related to the number of unpaired spins (N(s)) and calculate the binding and the activation energies involved in O(2) evolution for fixed values of N(s). In addition to keeping N(s) constant, we assume that reactions in which the N(s) of the reactants differs from that of the products are very slow. The potential energy surfaces obtained in this way depend strongly on N(s). For example, O(2) dissociation at the vacancy site on a clean partially reduced TiO(2)(110) surface is exothermic by 0.85 eV in the triplet state and the highest activation energy in the chain of reactions leading to the O(2) dissociation is 0.67 eV. In the singlet state, O(2) dissociation is endothermic by 0.11 eV and the activation energy leading to dissociation is 1.30 eV. These observations are in qualitative agreement with scanning tunneling microscopy experiment in which O(2) dissociation on a partially reduced rutile TiO(2)(110) surface is observed at temperature as low as 120 K. In contrast, O(2) dissociation is predicted to be endothermic and is prevented by an activation barrier larger than 1 eV in all the previous DFT calculations, in which the DFT program varies N(s) to get the lowest energy state. We find that on a partially reduced rutile TiO(2)(110) with Au(1) and Au(2) preadsorbed on its surface, O(2) dissociates at the vacancy site: One oxygen atom fills the oxygen vacancy and the other becomes available for oxidation chemistry. This means that Au(1) and Au(2) supported on a partially reduced TiO(2)(110) surface is not an oxidation catalyst since the presence of oxygen turns it into a stoichiometric Au(n)/TiO(2)(110) surface. Finally, we find that the evolution of oxygen on

Nitrogen-doped TiO2 materials have been shown to exhibit visible-light photoactivity, but the operative mechanism(s) are not well understood. Here we use structurally and compositionally well-defined epitaxial films of TiO2-xNx anatase (001) and rutile (110) (x≤~0.02) to show a qualitative difference between the visible-light activities for the two polymorphs. Holes generated by visible light at N sites in anatase (001) readily diffuse to the surface and oxidize adsorbed trimethyl acetate while the same in rutile (110) remain trapped in the bulk. In light of the low doping densities that can be achieved in phase-pure material, conventional wisdom suggests that holes should be trapped at N sites in both polymorphs. Although the detailed mechanism is not yet understood, these results suggest that the hole hopping probability is much higher along the [001] direction in N-doped anatase than along the [110] direction in N-doped rutile.

We present a novel scheme to construct a polarizable force field for liquid/solid interfaces, which takes into account the effect of the surface polarity induced by liquid-solid interactions explicitly. We extend the charge response kernel (CRK) method for molecules to solid surfaces by introducing the surface CRK. The CRK parameters are systematically determined by the first-principles calculations in the slab model with the dipole-correction method. Our methodology is applied to the water/clean rutile TiO2(110) interface. Structures and induced charges of a single water molecule attached to the TiO2 surface optimized by our polarizable force field show good agreement with those predicted by the first-principles calculations. Further, we carried out MD simulations for the liquid water/TiO2 interface and found three stable structures of water attached to the TiO2 surface. Two of them are predicted by both the polarizable and the nonpolarizable force fields, while the polarizable force field model predicts a structure of water with the hydrogen and oxygen atoms interacting with the oxygen atom of the surface TiO2 and the hydrogen atom of the other water molecule, respectively, which was reported by the previous first-principles MD simulation. This indicates that the dipole moments of water and TiO2 induced by the water-TiO2 interactions have significant impact on molecular conformations of the water/TiO2 interface.

The construction of nanocrystals with controllable composition and desirable micro-nanostructures is a well-known challenge. A combination of favorable composition and optimized micro-nanostructures can enhance the performance of a material significantly. Using TiO(2) as an example, we demonstrate here a facile approach to prepare anatase/rutile mixed-phase TiO(2) hollow micro-nanospheres with hierarchical mesopores. Our strategy relies on polymer-assisted assembly of ∼ 5 nm nano-building blocks into three-dimensional hierarchical hollow micro-nanospheres in a mixed alcohol-water solution. This superior micro-nanostructure endows the sample with hierarchical mesopores and a high surface area of 106 m(2) g(-1). We also show that, due to the synergetic effects of the mixed-phase composition and the micro-nanostructures, the sample exhibited significantly improved photovoltaic performance and similar photocatalytic performance compared with the commercial Degussa P25. These results suggested that our sample has great potential for future photovoltaic and photocatalytic applications.

Alkali-metal-ion extraction reactions using poly(tetrafluoroethylene) (PTFE; AEP reactions) were performed on two kinds of α-NaFeO(2)-type layered compounds: Na(0.68)(Li(0.68/3)Ti(1-0.68/3))O(2) and K(0.70)(Li(0.70/3)Sn(1-0.70/3))O(2). At 400 °C in flowing argon, these layered compounds were reacted with PTFE. By these reactions, alkali-metal ions in the layered compounds were successfully extracted, and TiO(2) and SnO(2) with rutile-type structure were formed. The structural similarity between the alkali-metal-ion-extracted layered compounds and the binary metal oxide products in these unique alkali-metal-ion extraction reactions was interpreted in terms of their interatomic distance distribution by atomic pair distribution function analysis. The results of this study indicate that PTFE is an effective agent to extract alkali-metal ions from layered compounds, and AEP reaction is not limited to the previously reported γ-FeOOH-type layered titania K(0.8)(Li(0.27)Ti(1.73))O(4), but is also applicable to other layered titania and other non-titanium-based layered metal oxides. Therefore, it was clarified that AEP reactions are widely applicable routes to prepare various compounds, including those that are difficult to synthesize by other reactions.

To explore metal oxide-oxide support interactions and their effects, the mechanism of CO oxidation on PdO catalysts with rutile TiO2 or TiO2-x (TiO2 with a bridging oxygen vacancy) as the support, was studied by density functional theory calculations, compared with that on pure PdO surface. For TiO2 as the support, support effect leads to the change of the preferential CO adsorption sites from the coordinatively unsaturated Pd (Pdcus) site on pure PdO surface to the bridging site of coordinatively unsaturated Pd and O atoms (Pdcus and Ocus), thus altering the reaction pathway of CO oxidation, whereas the support effect has little influence on the energy barrier. However, for TiO2-x as the support, the presence of the oxygen vacancy leads to the energy barrier remarkably decreased compared with that on pure or TiO2-supported PdO surface. The change of Bader charges indicates the oxygen vacancy in the support can tune the oxidizability of PdO surface active oxygen Ocus, thus adjusting the CO adsorption strength at the bridging site of Pdcus and Ocus to be favorable for the extraction process of Ocus. Tuning oxygen vacancies in supports can be used as a new perspective to design improved supported oxide catalysts.

Ultrathin dual phase nanosheets consisting of alternating spinel Li4Ti5O12 (LTO) and rutile TiO2 (RT) lamellas are synthesized through a facile and scalable hydrothermal method, and the formation mechanism is explored. The thickness of constituent lamellas can be controlled exactly by adjusting the mole ratio of Li:Ti in the original reactants. Alternating insertion of the RT lamellas significantly improves the electrochemical performance of LTO nanosheets, especially at high charge/discharge rates. As anodes in lithium-ion batteries (LIBs), the dual phase nanosheet electrode with the optimized phase ratio can deliver stable discharge capacities of 178.5, 154.9, 148.4, 142.3, 138.2, and 131.4 mA h g(-1) at current densities of 1, 10, 20, 30, 40, and 50 C, respectively. Meanwhile, they inherit the excellent cyclic stability of pure spinel LTO and exhibit a capacity retention of 93.1% even after 500 cycles at 50 C. Our results indicate that the alternating nanoscaled lamella structure is a good alternative to facilitate the transfer of both the Li ions and electrons into the spinel LTO, giving rise to an excellent cyclability and fast rate performance. Therefore, the newly prepared carbon-free LTO-RT nanosheets with high safety provide a new opportunity to develop high-power anodes for LIBs.

A new spectral restoration algorithm of reflection electron energy loss spectra is proposed. It is based on the maximum likelihood principle as implemented in the iterative Lucy-Richardson approach. Resolution is enhanced and point spread function recovered in a semi-blind way by forcing cyclically the zero loss to converge towards a Dirac peak. Synthetic phonon spectra of TiO{sub 2} are used as a test bed to discuss resolution enhancement, convergence benefit, stability towards noise, and apparatus function recovery. Attention is focused on the interplay between spectral restoration and quasi-elastic broadening due to free carriers. A resolution enhancement by a factor up to 6 on the elastic peak width can be obtained on experimental spectra of TiO{sub 2}(110) and helps revealing mixed phonon/plasmon excitations.

The electron paramagnetic resonance (EPR) g factor formulas for Cr5+ and V4+ ions in Al2O3, TiO2 and VO2 crystals are deduced from Jahn-Teller effect and contributions of the charge transfer (CT) levels. The tetragonal distortions. ΔR(R∥- R⊥) = -0.0184,-0.0045 and -0.0124 nm, and Δ𝜃 = 0∘, - 0.001∘ and 0∘, for Al2O3:Cr5+, TiO2:V4+ and VO2, respectively. The calculations of the g factors agree well with the experimental values. The contributions of the CT levels to g factors increase with the increasing valence state. It must be taken into account in the precise calculations of g factors for the high valence state d1 ions in crystals.

The structure solution of the modulated, delafossite-related, orthorhombic Ga3–xIn3TixO9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A3–xIn3TixO9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga1.5In3Ti1.5O9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga3-xIn3TixO9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ~3.4 eV before a ~0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ~3.0 eV. Resistance to oxidation and reduction is also presented.

The understanding about the utilization of experimental animals in scientific research and in teaching is many times a complex issue. Special attention needs to be paid to attain the understanding by the general public of the importance of animal experimentation in experimental research and in undergraduate medical teaching. Experimental teaching and research based on the availability of animals for experimentation is important and necessary for the personal and scientific development of the physician-to-be. The technological arsenal which intends to mimic experimentation animals and thus fully replace their use many times does not prove to be compatible with the reality of the living animal. The purpose of this paper is to discuss aspects concerning this topic, bringing up an issue which is complex and likely to arouse in-depth reflections.

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provide a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geologic conditions up to ~20 kbar (Thomas et al. (2010) Contrib Mineral Petrol 160, 743-759). One of the greatest limitations to analyzing Ti in metamorphic quartz by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is the lack of a suitable matrix-matched reference material. Typically LA-ICP-MS analyses of Ti in minerals use 49Ti as a normalizing mass because of an isobaric interference from 48Ca, which is present in most well characterized reference glasses, on 48Ti. The benefit of using a matrix-matched reference material to analyze Ti in quartz is the opportunity to use 48Ti (73.8 % abundance) as a normalizing mass, which results in an order of magnitude increase in signal strength compared to the less abundant isotope 49Ti (5.5 % abundance), thereby increasing the analytical precision. Here we characterize Ti-bearing SiO2 glasses from Heraeus Quarzglas and natural quartz grains from the Bishop Tuff by cathodoluminescence (CL) imaging, electron probe microanalysis (EPMA), and LA-ICP-MS, in order to determine their viability as reference materials for Ti in quartz. Titanium contents in low-CL rims in the Bishop Tuff quartz grains were determined to be homogenous by EPMA (41 ± 2 µg/g Ti, 2σ), and are a potential natural reference material. We present a new method for determining 48Ti concentrations in quartz by LA-ICP-MS at the 1 µg/g level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the homogeneous low-CL rims of the Bishop Tuff quartz are more suitable than NIST reference glasses as an in-house reference material for low Ti concentrations because matrix effects are limited and Ca isobaric interferences are avoided, thus allowing for the use of 48Ti as a normalizing mass. Titanium concentration from 33 analyses of low

"The Experimental College" tells the story of a 4-year academic experiment at the University of Wisconsin established by Alexander Meiklejohn. Aimed at finding a method of teaching that would help students develop "intelligence in the conduct of their own lives," the Experimental College discarded major requirements,…

Experimental oil spills are an essential component of overall oil pollution research efforts. However, such experiments must be carefully designed and coordinated in order to cull the most information possible. Physical, biological, and ecological impacts must be examined simultaneously. Long-term monitoring of the multidisciplinary effects of experimental oil spills is recommended.

The paper is a philosophical analysis of experimentation. The philosophical framework of the analysis is the interrogative model of inquiry developed by Hintikka. The basis of the model is explicit and well-formed logic of questions and answers. The framework allows us to formulate a flexible logic of experimentation. In particular, the formulated…

The results for an experimental study of a one wavelength MHD induction generator operating on a liquid flow are presented. First the design philosophy and the experimental generator design are summarized, including a description of the flow loop and instrumentation. Next a Fourier series method of treating the fact that the magnetic flux density produced by the stator is not a pure traveling sinusoid is described and some results summarized. This approach appears to be of interest after revisions are made, but the initial results are not accurate. Finally, some of the experimental data is summarized for various methods of excitation.

In the last few years a new line of research has appeared in the literature. This line of research, which may be referred to as experimental semiotics (ES; Galantucci, 2009; Galantucci and Garrod, 2010), focuses on the experimental investigation of novel forms of human communication. In this review we will (a) situate ES in its conceptual context, (b) illustrate the main varieties of studies thus far conducted by experimental semioticians, (c) illustrate three main themes of investigation which have emerged within this line of research, and (d) consider implications of this work for cognitive neuroscience. PMID:21369364

This final talk of the meeting briefly discussed a number of experimental topics that the author found particularly interesting in the area of High Energy Physics. It also includes some critical comments about the future direction of their discipline.

Boson sampling is a computational task strongly believed to be hard for classical computers, but efficiently solvable by orchestrated bosonic interference in a specialized quantum computer. Current experimental schemes, however, are still insufficient for a convincing demonstration of the advantage of quantum over classical computation. A new variation of this task, scattershot boson sampling, leads to an exponential increase in speed of the quantum device, using a larger number of photon sources based on parametric down-conversion. This is achieved by having multiple heralded single photons being sent, shot by shot, into different random input ports of the interferometer. We report the first scattershot boson sampling experiments, where six different photon-pair sources are coupled to integrated photonic circuits. We use recently proposed statistical tools to analyze our experimental data, providing strong evidence that our photonic quantum simulator works as expected. This approach represents an important leap toward a convincing experimental demonstration of the quantum computational supremacy. PMID:26601164

This information package was prepared for both new and experienced users of the SPHINX (Short Pulse High Intensity Nanosecond X-radiator) flash X-Ray facility. It was compiled to help facilitate experiment design and preparation for both the experimenter(s) and the SPHINX operational staff. The major areas covered include: Recording Systems Capabilities,Recording System Cable Plant, Physical Dimensions of SPHINX and the SPHINX Test cell, SPHINX Operating Parameters and Modes, Dose Rate Map, Experiment Safety Approval Form, and a Feedback Questionnaire. This package will be updated as the SPHINX facilities and capabilities are enhanced.

The paper is a philosophical analysis of experimentation. The philosophical framework of the analysis is the interrogative model of inquiry developed by Hintikka. The basis of the model is explicit and well-formed logic of questions and answers. The framework allows us to formulate a flexible logic of experimentation. In particular, the formulated model can be interpreted realistically. Moreover, the model demonstrates an explicit logic of knowledge acquisition. So, the natural extension of the model is to apply it to an analysis of the learning process.

Experimental searches for axions or axion-like particles rely on semiclassical phenomena resulting from the postulated coupling of the axion to two photons. Sensitive probes of the extremely small coupling constant can be made by exploiting familiar, coherent electromagnetic laboratory techniques, including resonant enhancement of transitions using microwave and optical cavities, Bragg scattering, and coherent photon-axion oscillations. The axion beam may either be astrophysical in origin as in the case of dark matter axion searches and solar axion searches, or created in the laboratory from laser interactions with magnetic fields. This note is meant to be a sampling of recent experimental results.

In the early twentieth century, Alexander Meiklejohn believed the undergraduate college must teach students how to think. He aspired to make students into thinking, caring, active citizens with the intellectual skills to participate in a democratic society. In 1927, with the founding of the Experimental College at the University of Wisconsin, he…

The authors bring together the results of several years of experimental work in drainage basin evolution, hydrology, river-channel morphology, and sedimentology. These investigations are related to real-world applications, particularly geological exploration and mapping. This text shows how awareness of natural phenomena can improve management of the natural environment, such as the control of rivers and eroding gullies.

Four experiments examined when laypeople attribute unexpected experimental outcomes to error, in foresight and in hindsight, along with their judgments of whether the data should be published. Participants read vignettes describing hypothetical experiments, along with the result of the initial observation, considered as either a possibility…

A method of housing experimental animals such as mice in individual tube- like plastic enclosures is described. Contrary to experience, when this was tried with metal the mice did not become panicky. Group housing, with its attendant difficulties, may thus be dispensed with. (AEC)

The following administrative aspects of scientific experimentation with human subjects are discussed: the definition of human experimentation; the distinction between experimentation and treatment; investigator responsibility; documentation; the elements and principles of informed consent; and the administrator's role in establishing and…

Rodent gerontology experiments should be carefully designed and correctly analyzed so as to provide the maximum amount of information for the minimum amount of work. There are five criteria for a "good" experimental design. These are applicable both to in vivo and in vitro experiments: (1) The experiment should be unbiased so that it is possible to make a true comparison between treatment groups in the knowledge that no one group has a more favorable "environment." (2) The experiment should have high precision so that if there is a true treatment effect there will be a good chance of detecting it. This is obtained by selecting uniform material such as isogenic strains, which are free of pathogenic microorganisms, and by using randomized block experimental designs. It can also be increased by increasing the number of observations. However, increasing the size of the experiment beyond a certain point will only marginally increase precision. (3) The experiment should have a wide range of applicability so it should be designed to explore the sensitivity of the observed experimental treatment effect to other variables such as the strain, sex, diet, husbandry, and age of the animals. With in vitro data, variables such as media composition and incubation times may also be important. The importance of such variables can often be evaluated efficiently using "factorial" experimental designs, without any substantial increase in the overall number of animals. (4) The experiment should be simple so that there is little chance of groups becoming muddled. Generally, formal experimental designs that are planned before the work starts should be used. (5) The experiment should provide the ability to calculate uncertainty. In other words, it should be capable of being statistically analyzed so that the level of confidence in the results can be quantified.

The accuracy and precision of pressure measurements and the pursuit of reliable and readily available pressure scales at simultaneous high temperatures and pressures are still topics in development in high pressure research despite many years of work. In situ pressure scales based on x-ray diffraction are widely used but require x-ray access, which is lacking outside of x-ray beam lines. Other methods such as fixed points require several experiments to bracket a pressure calibration point. In this study, a recoverable high-temperature pressure gauge for pressures ranging from 3 GPa to 10 GPa is presented. The gauge is based on the pressure-dependent solubility of an SiO{sub 2} component in the rutile-structured phase of GeO{sub 2} (argutite), and is valid when the argutite solid solution coexists with coesite. The solid solution varies strongly in composition, mainly in pressure but also somewhat in temperature, and the compositional variations are easily detected by x-ray diffraction of the recovered products because of significant changes in the lattice parameters. The solid solution is measured here on two isotherms, one at 1200 °C and the other at 1500 °C, and is developed as a pressure gauge by calibrating it against three fixed points for each temperature and against the lattice parameter of MgO measured in situ at a total of three additional points. A somewhat detailed thermodynamic analysis is then presented that allows the pressure gauge to be used at other temperatures. This provides a way to accurately and reproducibly evaluate the pressure in high pressure experiments and applications in this pressure-temperature range, and could potentially be used as a benchmark to compare various other pressure scales under high temperature conditions. - Graphical abstract: The saturation curve of SiO{sub 2} in TiO{sub 2} shows a strong pressure dependence and a strong dependence of unit cell volume on composition. This provides an opportunity to use this

Geoengineering is defined as the 'deliberate and large-scale intervention in the Earth's climatic system with the aim of reducing global warming'. The technological proposals for doing this are highly speculative. Research is at an early stage, but there is a strong consensus that technologies would, if realisable, have profound and surprising ramifications. Geoengineering would seem to be an archetype of technology as social experiment, blurring lines that separate research from deployment and scientific knowledge from technological artefacts. Looking into the experimental systems of geoengineering, we can see the negotiation of what is known and unknown. The paper argues that, in renegotiating such systems, we can approach a new mode of governance-collective experimentation. This has important ramifications not just for how we imagine future geoengineering technologies, but also for how we govern geoengineering experiments currently under discussion.

Temporal steering is a form of temporal correlation between the initial and final state of a quantum system. It is a temporal analogue of the famous Einstein-Podolsky-Rosen (spatial) steering. We demonstrate, by measuring the photon polarization, that temporal steering allows two parties to verify if they have been interacting with the same particle, even if they have no information about what happened with the particle in between the measurements. This is the first experimental study of temporal steering. We also performed experimental tests, based on the violation of temporal steering inequalities, of the security of two quantum key distribution protocols against individual attacks. Thus, these results can lead to applications for secure quantum communications and quantum engineering.

Temporal steering is a form of temporal correlation between the initial and final state of a quantum system. It is a temporal analogue of the famous Einstein-Podolsky-Rosen (spatial) steering. We demonstrate, by measuring the photon polarization, that temporal steering allows two parties to verify if they have been interacting with the same particle, even if they have no information about what happened with the particle in between the measurements. This is the first experimental study of temporal steering. We also performed experimental tests, based on the violation of temporal steering inequalities, of the security of two quantum key distribution protocols against individual attacks. Thus, these results can lead to applications for secure quantum communications and quantum engineering. PMID:27901121

The methods and techniques for experiment development and integration that evolved during the Skylab Program are described to facilitate transferring this experience to experimenters in future manned space programs. Management responsibilities and the sequential process of experiment evolution from initial concept through definition, development, integration, operation and postflight analysis are outlined in the main text and amplified, as appropriate, in appendixes. Emphasis is placed on specific lessons learned on Skylab that are worthy of consideration by future programs.

In this talk, I will review how a set of experiments in the last decade has given us our current understanding of neutrino properties.Â I will show how experiments in the last year or two have clarified this picture, and will discuss how new experiments about to start will address remaining questions.Â I will particularly emphasizeÂ the relationship between various experimental techniques.

The work of J. F. Woodward (1990 1996a; 1996b; 1998; 2002a; 2002b; 2004) on the existence of ``mass fluctuations'' and their use in exotic propulsion schemes was examined for possible application in improving space flight propulsion and power generation. Woodward examined Einstein's General Relativity Theory (GRT) and assumed that if the strong Machian interpretation of GRT as well as gravitational / inertia like Wheeler-Feynman radiation reaction forces hold, then when an elementary particle is accelerated through a potential gradient, its rest mass should fluctuate around its mean value during its acceleration. Woodward also used GRT to clarify the precise experimental conditions necessary for observing and exploiting these mass fluctuations or ``Woodward effect'' (W-E). Later, in collaboration with his ex-graduate student T. Mahood, they also pushed the experimental verification boundaries of these proposals. If these purported mass fluctuations occur as Woodward claims, and his assumption that gravity and inertia are both byproducts of the same GRT based phenomenon per Mach's Principle is correct, then many innovative applications such as propellantless propulsion and gravitational exotic matter generators may be feasible. This paper examines the reality of mass fluctuations and the feasibility of using the W-E to design propellantless propulsion devices in the near to mid-term future. The latest experimental results, utilizing MHD-like force rectification systems, will also be presented.

According to the paleomagnetic analysis there are variations of Earth’s magnetic field connected with magnetic moment changing. These variations affect on the South Atlantic Anomaly (SAA) location. Indeed different observations approved the existence of the SAA westward drift rate (0.1 1.0 deg/year) and northward drift rate (approximately 0.1 deg/year). In this work, we present the analysis of experimental results obtained in Scobeltsyn Institute of Nuclear Physics, Moscow State University (SINP MSU) onboard different Earth’s artificial satellites (1972 2003). The fluxes of protons with energy >50 MeV, gamma quanta with energy >500 keV and neutrons with energy 0.1 1.0 MeV in the SAA region have been analyzed. The mentioned above experimental data were obtained onboard the orbital stations Salut-6 (1979), MIR (1991, 1998) and ISS (2003) by the similar experimental equipment. The comparison of the data obtained during these two decades of investigations confirms the fact that the SAA drifts westward. Moreover the analysis of fluxes of electrons with energy about hundreds keV (Cosmos-484 (1972) and Active (Interkosmos-24, 1991) satellites) verified not only the SAA westward drift but northward drift also.

Experimental models of genetic hypertension are used to develop paradigms to study human essential hypertension while removing some of the complexity inherent in the study of human subjects. Since 1991 several quantitative trait loci responsible for blood pressure regulation have been identified in various rat crosses. More recently, a series of interesting quantitative trait loci influencing cardiac hypertrophy, stroke, metabolic syndrome and renal damage has also been described. It is recognized that the identification of large chromosomal regions containing a quantitative trait locus is only a first step towards gene identification. The next step is the production of congenic strains and substrains to confirm the existence of the quantitative trait locus and to narrow down the chromosomal region of interest. Several congenic strains have already been produced, with further refinement of the methodology currently in progress. The ultimate goal is to achieve positional cloning of the causal gene, a task which has so far been elusive. There are several areas of cross-fertilization between experimental and human genetics of hypertension, with a successful transfer of two loci directly from rats to humans and with new pharmacogenetic approaches which may be utilized in both experimental and clinical settings.

Experimental data are presented with respect to "experimental alcohol blastopathy" performed in our laboratory. As in our interpretation the notion of blastopathy involves both pathological changes during preimplantation development due to previous, preconceptional or preimplantation influences and later, pre- or postnatal effects induced by factors active during the preimplantation period, up to now the following experimental models were applied (on rats and mice): chronic and acute maternal, biparental or paternal ethanol alcoholization; preimplantation treatment with acetaldehyde or disulfiram followed by ethanol administration; acute ethanol intoxication before implantation on the background of chronic maternal ethanol intake; chronic maternal intake of various beverages. The main components of experimental alcohol blastopathy detected (by using a complex control methodology) were: pathological changes during the preimplantation developmental stages (lower mean number of embryos/animal, retardation of development, lowered migration rate of the embryos from the oviduct to the uterus, higher number of pathological morphological features), delayed implantation, disturbances of the early postimplantation development, retarded late foetal and placental growth. The effect of ethanol may be direct (ethanol being detectable in the oviductal and uterine fluid after both acute and chronic alcoholization) or indirect, via changes of the maternal macro- or microenvironment. The increase of the maternal blood acetaldehyde level may contribute to the appearance of alcohol blastopathy. Chronic beer and wine intake and acute intoxication with cognac suggest - up to now - the enhancing effect of beverage congeners. The noxious effect of acute ethanol intoxication superposed to chronic alcoholization is more marked that the separate effect of the two kinds of treatment. The chronic ethanol intake of fertilizing males (in mice) leads, both in the case of treated or untreated

The experimental air turbine VT400 is located in hall laboratories of the Department of Power System Engineering. It is a single-stage air turbine located in the suction of the compressor. It is able to solve various problems concerning the construction solution of turbine stages. The content of the article will deal mainly with the description of measurements on this turbine. The up-to-now research on this test rig will be briefly mentioned, too, as well as the description of the ongoing reconstruction.

Illustrating the complexity of the stress response and its multifaceted manifestations is the leading idea of this overview of experimental paradigms used for stress induction in laboratory animals. The description of key features of models based on naturalistic stressors, pharmacological challenges, and genomic manipulations is complemented by comprehensive analysis of physiological, behavioral, neurochemical, and endocrine changes and their appropriatness as outcome readouts. Particular attention has been paid to the role of sex and age as determinants of the dynamics of the stress response. Possible translational applications of stress-inducing paradigms as models of disease are briefly sketched. PMID:17290800

A device for watering experimental animals confined in a battery of individual plastic enclosures is described. It consists of a rectangular plastic enclosure having a plurality of fluid-tight compartments, each with a drinking hole near the bottom and a filling hole on the top. The enclosure is immersed in water until filled, its drinking holes sealed with a strip of tape, and it is then placed in the battery. The tape sealing prevents the flow of water from the device, but permits animals to drink by licking the drinking holes. (AEC)

With the development of new technologies for simultaneous analysis of many genes, transcripts, or proteins (the "omics" revolution), it has become common to outsource parts of the experimental work. In order to maintain the integrity of the research projects, it is important that the interphase between the researcher and the service is further developed. This involves robust protocols for sample preparation, an informed choice of analytical tool, development of standards for individual technologies, and transparent data analysis. This chapter introduces some of the problems related to analysis of RNA samples in the "omics" context and gives a few hints and key references related to sample preparation for the non-specialist.

In 1994 the Israeli parliament (Knesset) amended the Cruelty to Animals Act to regulate the use of experimental animals. Accordingly, animal experiments can only be carried out for the purposes of promoting health and medical science, reducing suffering, advancing scientific research, testing or production of materials and products (excluding cosmetics and cleaning products) and education. Animal experiments are only permitted if alternative methods are not possible. The National Board for Animal Experimentation was established to implement the law. Its members are drawn from government ministries, representatives of doctors, veterinarians, and industry organizations, animal rights groups, and academia. In order to carry out an animal experiment, the institution, researchers involved, and the specific experiment, all require approval by the Board. To date the Board has approved some 35 institutions, about half are public institutions (universities, hospitals and colleges) and the rest industrial firms in biotechnology and pharmaceutics. In 2000, 250,000 animals were used in research, 85% were rodents, 11% fowls, 1,000 other farm animals, 350 dogs and cats, and 39 monkeys. Academic institutions used 74% of the animals and industry the remainder. We also present summarized data on the use of animals in research in other countries.

KEKADA, a system that is capable of carrying out a complex series of experiments on problems from the history of science, is described. The system incorporates a set of experimentation strategies that were extracted from the traces of the scientists' behavior. It focuses on surprises to constrain its search, and uses its strategies to generate hypotheses and to carry out experiments. Some strategies are domain independent, whereas others incorporate knowledge of a specific domain. The domain independent strategies include magnification, determining scope, divide and conquer, factor analysis, and relating different anomalous phenomena. KEKADA represents an experiment as a set of independent and dependent entities, with apparatus variables and a goal. It represents a theory either as a sequence of processes or as abstract hypotheses. KEKADA's response is described to a particular problem in biochemistry. On this and other problems, the system is capable of carrying out a complex series of experiments to refine domain theories. Analysis of the system and its behavior on a number of different problems has established its generality, but it has also revealed the reasons why the system would not be a good experimental scientist.

Acute pancreatitis is an inflammatory disease characterized by interstitial edema, inflammatory cell infiltration, and acinar cell necrosis, depending on its severity. Regardless of the extent of tissue injury, acute pancreatitis is a completely reversible process with evident normal tissue architecture after recovery. Its pathogenic mechanism has been known to be closely related to intracellular digestive enzyme activation. In contrast to acute pancreatitis, chronic pancreatitis is characterized by irreversible tissue damage such as acinar cell atrophy and pancreatic fibrosis that results in exocrine and endocrine insufficiency. Recently, many studies of chronic pancreatitis have been prompted by the discovery of the pancreatic stellate cell, which has been identified and distinguished as the key effector cell of pancreatic fibrosis. However, investigations into the pathogenesis and treatment of pancreatitis face many obstacles because of its anatomical location and disparate clinical course. Due to these difficulties, most of our knowledge on pancreatitis is based on research conducted using experimental models of pancreatitis. In this review, several experimental models of pancreatitis will be discussed in terms of technique, advantages, and limitations. PMID:24944983

I was asked to discuss future experimental programs even though I am a theorist. As a result, I present my own personal views on where the field is, and where it is going, based on what I myself have been working on. In particular, I discuss why we need expeditions into high energies to find clues to where the relevant energy scale is for dark matter, baryon asymmetry and neutrino mass. I also argue that the next energy frontier machine should be justified on the basis of what we know, namely the mass of the Higgs boson, so that we will learn what energy we should aim at once we nail the Higgs sector. Finally, I make remarks on dark energy.

Traumatic brain injury, a leading cause of death and disability, is a result of an outside force causing mechanical disruption of brain tissue and delayed pathogenic events which collectively exacerbate the injury. These pathogenic injury processes are poorly understood and accordingly no effective neuroprotective treatment is available so far. Experimental models are essential for further clarification of the highly complex pathology of traumatic brain injury towards the development of novel treatments. Among the rodent models of traumatic brain injury the most commonly used are the weight-drop, the fluid percussion, and the cortical contusion injury models. As the entire spectrum of events that might occur in traumatic brain injury cannot be covered by one single rodent model, the design and choice of a specific model represents a major challenge for neuroscientists. This review summarizes and evaluates the strengths and weaknesses of the currently available rodent models for traumatic brain injury. PMID:20707892

Because of their large population sizes and rapid cell division rates, marine microbes have, or can generate, ample variation to fuel evolution over a few weeks or months, and subsequently have the potential to evolve in response to global change. Here we measure evolution in the marine diatom Skeletonema marinoi evolved in a natural plankton community in CO2-enriched mesocosms deployed in situ. Mesocosm enclosures are typically used to study how the species composition and biogeochemistry of marine communities respond to environmental shifts, but have not been used for experimental evolution to date. Using this approach, we detect a large evolutionary response to CO2 enrichment in a focal marine diatom, where population growth rate increased by 1.3-fold in high CO2-evolved lineages. This study opens an exciting new possibility of carrying out in situ evolution experiments to understand how marine microbial communities evolve in response to environmental change. PMID:25833241

The integration of information from various sensory systems is one of the most difficult challenges in understanding both perception and cognition. For example, the problem of auditory-visual integration is a correspondence problem between perceived auditory and visual scenes. Two main questions arise when designing data analysis systems: what is the useful information to be integrated?, and what are the integration rules? The problem of integrating information becomes relevant whenever: (a) the same kind of data are detected by spatially distributed sensors; (b) heterogeneous data are detected by different sensors; (c) heterogeneous distributed data are involved. General problems concerning the integration of experimental data are reviewed. The case of the BeppoSAX X-ray astronomical satellite is given as an example.

Adaptive measurements were recently shown to significantly improve the performance of quantum state tomography. Utilizing information about the system for the online choice of optimal measurements allows one to reach the ultimate bounds of precision for state reconstruction. In this article we generalize an adaptive Bayesian approach to the case of process tomography and experimentally show its superiority in the task of learning unknown quantum operations. Our experiments with photonic polarization qubits cover all types of single-qubit channels. We also discuss instrumental errors and the criteria for evaluation of the ultimate achievable precision in an experiment. It turns out that adaptive tomography provides a lower noise floor in the presence of strong technical noise.

Basson's commentary on my proposals regarding the structure and function of research in bioethics provides a welcome opportunity for extended comparison of standard approaches with the suggestions made in 'What Bioethics Should Be.' I begin by noting a common assumption underlying our respective views. I then address points of fundamental difference, indicating why the experimental method proposed in my original essay presents a potentially more productive strategy for examining moral issues in biomedicine. In the latter respect, I certainly disagree with Basson's contention that "we are unable to test" metaethical hypotheses "against reality" (Basson, p. 185) - a proposition which seems no more defensible than the equally untenable claim that we cannot refine methods of natural science research through examination of their usefulness in advancing our understanding of the correlation of events in nature.

This paper presents a multi-microprocessor LISP machine whose goal is to exploit the inherent parallelism in the LISP programs fully. The base architecture is a MIMD architecture based on a hybrid model for combinating data driven, demand driven and VoN Neumann process schemes. The basic evaluation strategy is data driven. Lazy evaluation mechanism is introduced to avoid unnecessary and unsafe computations. An experimental system with the four processor elements has been built in HIT, China. The system consists of a Z80 microcomputer and three TP8O1s interconnected through three buses. Each processor evaluates a part of programs asynchronously. The shared memory is divided into two parts: list cell area and enviroment area, each of which has the indepen-dent common bus to avoid the bus bottleneck.

An understanding of impact processes in low- and microgravity environments would be advanced significantly by the construction and use of an impact facility on the Space Station. It is proposed that initial studies begin as soon as possible in ground-based impact laboratories, on the NASA KC-135 Reduced-Gravity Aircraft, and in existing drop towers. The resulting experience and information base could then be applied toward an experiment package designed for use on Shuttle orbiters to support pilot studies in orbital environments. These experiments, as well as the first efforts made on the IOC Space Station, should involve the impact of various free-floating targets; such studies would yield a substantial scientific return while providing valuable experience and engineering information for use in refining the design of the dedicated Space Station Impact Facility. The dedicated facility should be designed to support impact experimentation, including but not limited to cratering, asteroid and ring-particle dynamics, and accretional processes.

In this Letter we present the first implementation of a quantum coin-tossing protocol. This protocol belongs to a class of “two-party” cryptographic problems, where the communication partners distrust each other. As with a number of such two-party protocols, the best implementation of the quantum coin tossing requires qutrits, resulting in a higher security than using qubits. In this way, we have also performed the first complete quantum communication protocol with qutrits. In our experiment the two partners succeeded to remotely toss a row of coins using photons entangled in the orbital angular momentum. We also show the experimental bounds of a possible cheater and the ways of detecting him.

This article describes the sloshing experiment performed on the HYDRA multi-axis hydraulic shaker at ESTEC. Two tank geometries, a rectangular tank and a pill shaped tank, were excited in the lateral direction. Both tanks, manufactured from a transparent material in order to provide high visibility of the phenomenon, were filled with water and several fill ratios were tested, varying the amplitude of the input and the sweep rate. The results of the test are presented from a structural point of view, with the main objective to study the interface force due to dynamic fluid sloshing motion. An investigation of the behaviour of the water around the main resonance of the assembly is conducted through the observation of the identified modes and the damping values. The experimental results confirm the amplification effect at low frequency caused by water sloshing motion and a comparison with data from numerical simulation is provided.

Non-bonded interactions between model pesticides and organo-mineral surfaces have been studied using molecular mechanical conformational calculations and molecular dynamics simulations. The minimum energy conformations and relative binding energies for the interaction of atrazine...

The high energy physics group at the University of South Carolina, under the leadership of Profs. S.R. Mishra, R. Petti, M.V. Purohit, J.R. Wilson (co-PI's), and C. Rosenfeld (PI), engaged in studies in "Experimental Particle Physics." The group collaborated with similar groups at other universities and at national laboratories to conduct experimental studies of elementary particle properties. We utilized the particle accelerators at the Fermi National Accelerator Laboratory (Fermilab) in Illinois, the Stanford Linear Accelerator Center (SLAC) in California, and the European Center for Nuclear Research (CERN) in Switzerland. Mishra, Rosenfeld, and Petti worked predominantly on neutrino experiments. Experiments conducted in the last fifteen years that used cosmic rays and the core of the sun as a source of neutrinos showed conclusively that, contrary to the former conventional wisdom, the "flavor" of a neutrino is not immutable. A neutrino of flavor "e," "mu," or "tau," as determined from its provenance, may swap its identity with one of the other flavors -- in our jargon, they "oscillate." The oscillation phenomenon is extraordinarily difficult to study because neutrino interactions with our instruments are exceedingly rare -- they travel through the earth mostly unimpeded -- and because they must travel great distances before a substantial proportion have made the identity swap. Three of the experiments that we worked on, MINOS, NOvA, and LBNE utilize a beam of neutrinos from an accelerator at Fermilab to determine the parameters governing the oscillation. Two other experiments that we worked on, NOMAD and MIPP, provide measurements supportive of the oscillation experiments. Good measurements of the neutrino oscillation parameters may constitute a "low energy window" on related phenomena that are otherwise unobservable because they would occur only at energies way above the reach of conceivable accelerators. Purohit and Wilson participated in the BaBar experiment

We are continuing a research program in particle astrophysics and high energy experimental particle physics. We have joined the DUMAND Collaboration, which is constructing a deep undersea astrophysical neutrino detector near Hawaii. Studies of high energy hadronic interactions using emulsion chamber techniques were also continued, using balloon flight exposures to ultra-high cosmic ray nuclei (JACEE) and accelerator beams. As members of the DUMAND Collaboration, we have responsibility for development a construction of critical components for the deep undersea neutrino detector facility. We have designed and developed the acoustical positioning system required to permit reconstruction of muon tracks with sufficient precision to meet the astrophysical goals of the experiment. In addition, we are making significant contributions to the design of the database and triggering system to be used. Work has been continuing in other aspects of the study of multiparticle production processes in nuclei. We are participants in a joint US/Japan program to study nuclear interactions at energies two orders of magnitude greater than those of existing accelerators, using balloon-borne emulsion chambers. On one of the flights we found two nuclear interactions of multiplicity over 1000 -- one with a multiplicity of over 2000 and pseudorapidity density {approximately} 800 in the central region. At the statistical level of the JACEE experiment, the frequency of occurrence of such events is orders of magnitude too large. We have continued our ongoing program to study hadronic interactions in emulsions exposed to high energy accelerator beams.

Two chimpanzees were given by mouth large numbers of viable oocysts of Toxoplasma gondii obtained from the faeces of experimentally infected cats. Before the experiment the first chimpanzee had a positive dye test reaction (1:250), an indication that it had undergone an earlier infection of toxoplasmosis; the serum antibody titres remained unchanged, no evidence of illness was found, and oocysts did not appear in its faeces during the subsequent six weeks. The second chimpanzee showed a negative dye test reaction before infection, and this converted to positive on the 7th day, rose to a peak on the 35th day, and remained high for six months. This animal appeared unwell during the first week, and on the 7th day its blood proved infective to mice; on the 40th day the lymph nodes became enlarged and biopsy specimens of a node and muscle in the 11th week were also infective to mice. No oocysts were passed in the faeces. The presumed cycle in the chimpanzee and in man and the relationships between Toxoplasma and Isospora are discussed. PMID:5575975

Classical correlation can be locked via quantum means: quantum data locking. With a short secret key, one can lock an exponentially large amount of information in order to make it inaccessible to unauthorized users without the key. Quantum data locking presents a resource-efficient alternative to one-time pad encryption which requires a key no shorter than the message. We report experimental demonstrations of a quantum data locking scheme originally proposed by D. P. DiVincenzo et al. [Phys. Rev. Lett. 92, 067902 (2004), 10.1103/PhysRevLett.92.067902] and a loss-tolerant scheme developed by O. Fawzi et al. [J. ACM 60, 44 (2013), 10.1145/2518131]. We observe that the unlocked amount of information is larger than the key size in both experiments, exhibiting strong violation of the incremental proportionality property of classical information theory. As an application example, we show the successful transmission of a photo over a lossy channel with quantum data (un)locking and error correction.

Magnetite is an important iron ore mineral and the most prominent Fe-oxide phase in the Earth's crust. The systematic occurrence of magnetite in zones of intense deformation in oceanic core complexes suggests that it may play a role in strain localization in some silicate rocks. We performed a series of high-temperature deformation experiments on synthetic magnetite aggregates and natural single crystals to characterize the rheological behavior of magnetite. As starting material, we used fine-grained magnetite powder that was hot isostatically pressed at 1100°C for several hours, resulting in polycrystalline material with a mean grain size of around 40 μm and containing 3-5% porosity. Samples were deformed to 15-20% axial strain under constant load (approximating constant stress) conditions in a Paterson-type gas apparatus for triaxial deformation at temperatures between 900 and 1100°C and 300 MPa confining pressure. The aggregates exhibit typical power-law creep behavior. At high stresses, samples deformed by dislocation creep exhibit stress exponents close to 3, revealing a transition to near-Newtonian creep with stress exponents around 1.3 at lower stresses. Natural magnetite single crystals deformed at 1 atm pressure and temperatures between 950°C and 1150 °C also exhibit stress exponents close to 3, but with lower flow stresses and a lower apparent activation energy than the aggregates. Such behavior may result from the different oxygen fugacity buffers used. Crystallographic-preferred orientations in all polycrystalline samples are very weak and corroborate numerical models of CPO development, suggesting that texture development in magnetite may be inherently slow compared with lower symmetry phases. Comparison of our results with experimental deformation data for various silicate minerals suggests that magnetite should be weaker than most silicates during ductile creep in dry igneous rocks.